two compounding additives to improve tire reversion

43
Two Compounding Additives to Improve Tire Reversion Resistance Dr. Hermann-Josef Weidenhaupt, Joel Neilsen* Lanxess Corporation Presented at ITEC 2018, Akron, Ohio

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Two Compounding Additives to Improve Tire Reversion ResistanceDr Hermann-Josef Weidenhaupt Joel Neilsen LanxessCorporationPresented at ITEC 2018 Akron Ohio

Challenge

2

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

3

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

4

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

5

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

6

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

bull We will present features and performance of two Rhein Chemie products designed to reduce reversion Perkalinkreg900 and Vulcurenreg

7

8

Properties of Crosslink Structure

Advantages of short crosslinks (C-C- or C-S-C-bridges)minus Reversion stabilityheat stabilityminus Compression setpermanent set at elevated temperatures

Advantages of long crosslinks (C-Sx-C-bridges)minus Tensile strengthminus Rebound elasticityminus Tear resistanceminus Fatigue resistanceminus Dynamic damping

Figure 1 Sulfur Crosslinking of Polyisoprene

Sulfur Crosslinks Form at the Allylic Hydrogen Atoms

Figure 2 Changes in network structure during reversion

S

SS

SS

S

SS

S

AccS

S SSSS

S

S

AccS

S

S

SSSS

AccS S

S

SS S

S

S

bullBreakage of crosslinks

bullRearrangement Cyclisation

bullShortening of crosslinks

bullIsomerisation conjugated double bonds

bullNew crosslinks

SSSS

Reversion process

SS

SS

SxS

S

SS S

SxSy-ACC

type of sulfur bridge bonding energy (kJmol)- C - SX - C - (x gt 2) lt 268- C - S2 - C - 268- C - S - C - 285- C - C - 352

Figure 3 Crosslink Bonding Energy

Torq

ueS

lsquo [s

tand

ardi

zed]

07

08

09

10

0 50 100 150

VSL 5025-0 (SSBR)

VSL 2525-0 (SSBR)

CB 24 (BR)

Natsyn 2200

NR (Crepe)

SL 25-0 (SSBR)

160degC

Figure 4 Influence of polymer on reversion

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Challenge

2

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

3

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

4

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

5

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

6

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

bull We will present features and performance of two Rhein Chemie products designed to reduce reversion Perkalinkreg900 and Vulcurenreg

7

8

Properties of Crosslink Structure

Advantages of short crosslinks (C-C- or C-S-C-bridges)minus Reversion stabilityheat stabilityminus Compression setpermanent set at elevated temperatures

Advantages of long crosslinks (C-Sx-C-bridges)minus Tensile strengthminus Rebound elasticityminus Tear resistanceminus Fatigue resistanceminus Dynamic damping

Figure 1 Sulfur Crosslinking of Polyisoprene

Sulfur Crosslinks Form at the Allylic Hydrogen Atoms

Figure 2 Changes in network structure during reversion

S

SS

SS

S

SS

S

AccS

S SSSS

S

S

AccS

S

S

SSSS

AccS S

S

SS S

S

S

bullBreakage of crosslinks

bullRearrangement Cyclisation

bullShortening of crosslinks

bullIsomerisation conjugated double bonds

bullNew crosslinks

SSSS

Reversion process

SS

SS

SxS

S

SS S

SxSy-ACC

type of sulfur bridge bonding energy (kJmol)- C - SX - C - (x gt 2) lt 268- C - S2 - C - 268- C - S - C - 285- C - C - 352

Figure 3 Crosslink Bonding Energy

Torq

ueS

lsquo [s

tand

ardi

zed]

07

08

09

10

0 50 100 150

VSL 5025-0 (SSBR)

VSL 2525-0 (SSBR)

CB 24 (BR)

Natsyn 2200

NR (Crepe)

SL 25-0 (SSBR)

160degC

Figure 4 Influence of polymer on reversion

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

3

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

4

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

5

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

6

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

bull We will present features and performance of two Rhein Chemie products designed to reduce reversion Perkalinkreg900 and Vulcurenreg

7

8

Properties of Crosslink Structure

Advantages of short crosslinks (C-C- or C-S-C-bridges)minus Reversion stabilityheat stabilityminus Compression setpermanent set at elevated temperatures

Advantages of long crosslinks (C-Sx-C-bridges)minus Tensile strengthminus Rebound elasticityminus Tear resistanceminus Fatigue resistanceminus Dynamic damping

Figure 1 Sulfur Crosslinking of Polyisoprene

Sulfur Crosslinks Form at the Allylic Hydrogen Atoms

Figure 2 Changes in network structure during reversion

S

SS

SS

S

SS

S

AccS

S SSSS

S

S

AccS

S

S

SSSS

AccS S

S

SS S

S

S

bullBreakage of crosslinks

bullRearrangement Cyclisation

bullShortening of crosslinks

bullIsomerisation conjugated double bonds

bullNew crosslinks

SSSS

Reversion process

SS

SS

SxS

S

SS S

SxSy-ACC

type of sulfur bridge bonding energy (kJmol)- C - SX - C - (x gt 2) lt 268- C - S2 - C - 268- C - S - C - 285- C - C - 352

Figure 3 Crosslink Bonding Energy

Torq

ueS

lsquo [s

tand

ardi

zed]

07

08

09

10

0 50 100 150

VSL 5025-0 (SSBR)

VSL 2525-0 (SSBR)

CB 24 (BR)

Natsyn 2200

NR (Crepe)

SL 25-0 (SSBR)

160degC

Figure 4 Influence of polymer on reversion

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

4

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

5

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

6

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

bull We will present features and performance of two Rhein Chemie products designed to reduce reversion Perkalinkreg900 and Vulcurenreg

7

8

Properties of Crosslink Structure

Advantages of short crosslinks (C-C- or C-S-C-bridges)minus Reversion stabilityheat stabilityminus Compression setpermanent set at elevated temperatures

Advantages of long crosslinks (C-Sx-C-bridges)minus Tensile strengthminus Rebound elasticityminus Tear resistanceminus Fatigue resistanceminus Dynamic damping

Figure 1 Sulfur Crosslinking of Polyisoprene

Sulfur Crosslinks Form at the Allylic Hydrogen Atoms

Figure 2 Changes in network structure during reversion

S

SS

SS

S

SS

S

AccS

S SSSS

S

S

AccS

S

S

SSSS

AccS S

S

SS S

S

S

bullBreakage of crosslinks

bullRearrangement Cyclisation

bullShortening of crosslinks

bullIsomerisation conjugated double bonds

bullNew crosslinks

SSSS

Reversion process

SS

SS

SxS

S

SS S

SxSy-ACC

type of sulfur bridge bonding energy (kJmol)- C - SX - C - (x gt 2) lt 268- C - S2 - C - 268- C - S - C - 285- C - C - 352

Figure 3 Crosslink Bonding Energy

Torq

ueS

lsquo [s

tand

ardi

zed]

07

08

09

10

0 50 100 150

VSL 5025-0 (SSBR)

VSL 2525-0 (SSBR)

CB 24 (BR)

Natsyn 2200

NR (Crepe)

SL 25-0 (SSBR)

160degC

Figure 4 Influence of polymer on reversion

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

5

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

6

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

bull We will present features and performance of two Rhein Chemie products designed to reduce reversion Perkalinkreg900 and Vulcurenreg

7

8

Properties of Crosslink Structure

Advantages of short crosslinks (C-C- or C-S-C-bridges)minus Reversion stabilityheat stabilityminus Compression setpermanent set at elevated temperatures

Advantages of long crosslinks (C-Sx-C-bridges)minus Tensile strengthminus Rebound elasticityminus Tear resistanceminus Fatigue resistanceminus Dynamic damping

Figure 1 Sulfur Crosslinking of Polyisoprene

Sulfur Crosslinks Form at the Allylic Hydrogen Atoms

Figure 2 Changes in network structure during reversion

S

SS

SS

S

SS

S

AccS

S SSSS

S

S

AccS

S

S

SSSS

AccS S

S

SS S

S

S

bullBreakage of crosslinks

bullRearrangement Cyclisation

bullShortening of crosslinks

bullIsomerisation conjugated double bonds

bullNew crosslinks

SSSS

Reversion process

SS

SS

SxS

S

SS S

SxSy-ACC

type of sulfur bridge bonding energy (kJmol)- C - SX - C - (x gt 2) lt 268- C - S2 - C - 268- C - S - C - 285- C - C - 352

Figure 3 Crosslink Bonding Energy

Torq

ueS

lsquo [s

tand

ardi

zed]

07

08

09

10

0 50 100 150

VSL 5025-0 (SSBR)

VSL 2525-0 (SSBR)

CB 24 (BR)

Natsyn 2200

NR (Crepe)

SL 25-0 (SSBR)

160degC

Figure 4 Influence of polymer on reversion

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

6

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

bull We will present features and performance of two Rhein Chemie products designed to reduce reversion Perkalinkreg900 and Vulcurenreg

7

8

Properties of Crosslink Structure

Advantages of short crosslinks (C-C- or C-S-C-bridges)minus Reversion stabilityheat stabilityminus Compression setpermanent set at elevated temperatures

Advantages of long crosslinks (C-Sx-C-bridges)minus Tensile strengthminus Rebound elasticityminus Tear resistanceminus Fatigue resistanceminus Dynamic damping

Figure 1 Sulfur Crosslinking of Polyisoprene

Sulfur Crosslinks Form at the Allylic Hydrogen Atoms

Figure 2 Changes in network structure during reversion

S

SS

SS

S

SS

S

AccS

S SSSS

S

S

AccS

S

S

SSSS

AccS S

S

SS S

S

S

bullBreakage of crosslinks

bullRearrangement Cyclisation

bullShortening of crosslinks

bullIsomerisation conjugated double bonds

bullNew crosslinks

SSSS

Reversion process

SS

SS

SxS

S

SS S

SxSy-ACC

type of sulfur bridge bonding energy (kJmol)- C - SX - C - (x gt 2) lt 268- C - S2 - C - 268- C - S - C - 285- C - C - 352

Figure 3 Crosslink Bonding Energy

Torq

ueS

lsquo [s

tand

ardi

zed]

07

08

09

10

0 50 100 150

VSL 5025-0 (SSBR)

VSL 2525-0 (SSBR)

CB 24 (BR)

Natsyn 2200

NR (Crepe)

SL 25-0 (SSBR)

160degC

Figure 4 Influence of polymer on reversion

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Challenge

bull Large tires such as TruckBus Aircraft and tires used on giant loadingdump trucks have a large percentage of natural rubber in their compounds NR is necessary due to its toughness and lower hysteretic properties

bull It is well known that natural rubber will revert heat from vulcanization and heat from severe service will cause natural rubber to lose its physical properties (tensile modulus tear etc) This reversion can reduce the service life of large tires

bull Natural rubber reversion is primarily due to the breakdown of poly sulfidic crosslinks into shorter fewer crosslinks

bull The tires of focus tend to be far more expensive vs standard street tires so extending their service life is greatly desired and thus increasing reversion resistance is an important goal

bull We will present features and performance of two Rhein Chemie products designed to reduce reversion Perkalinkreg900 and Vulcurenreg

7

8

Properties of Crosslink Structure

Advantages of short crosslinks (C-C- or C-S-C-bridges)minus Reversion stabilityheat stabilityminus Compression setpermanent set at elevated temperatures

Advantages of long crosslinks (C-Sx-C-bridges)minus Tensile strengthminus Rebound elasticityminus Tear resistanceminus Fatigue resistanceminus Dynamic damping

Figure 1 Sulfur Crosslinking of Polyisoprene

Sulfur Crosslinks Form at the Allylic Hydrogen Atoms

Figure 2 Changes in network structure during reversion

S

SS

SS

S

SS

S

AccS

S SSSS

S

S

AccS

S

S

SSSS

AccS S

S

SS S

S

S

bullBreakage of crosslinks

bullRearrangement Cyclisation

bullShortening of crosslinks

bullIsomerisation conjugated double bonds

bullNew crosslinks

SSSS

Reversion process

SS

SS

SxS

S

SS S

SxSy-ACC

type of sulfur bridge bonding energy (kJmol)- C - SX - C - (x gt 2) lt 268- C - S2 - C - 268- C - S - C - 285- C - C - 352

Figure 3 Crosslink Bonding Energy

Torq

ueS

lsquo [s

tand

ardi

zed]

07

08

09

10

0 50 100 150

VSL 5025-0 (SSBR)

VSL 2525-0 (SSBR)

CB 24 (BR)

Natsyn 2200

NR (Crepe)

SL 25-0 (SSBR)

160degC

Figure 4 Influence of polymer on reversion

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

8

Properties of Crosslink Structure

Advantages of short crosslinks (C-C- or C-S-C-bridges)minus Reversion stabilityheat stabilityminus Compression setpermanent set at elevated temperatures

Advantages of long crosslinks (C-Sx-C-bridges)minus Tensile strengthminus Rebound elasticityminus Tear resistanceminus Fatigue resistanceminus Dynamic damping

Figure 1 Sulfur Crosslinking of Polyisoprene

Sulfur Crosslinks Form at the Allylic Hydrogen Atoms

Figure 2 Changes in network structure during reversion

S

SS

SS

S

SS

S

AccS

S SSSS

S

S

AccS

S

S

SSSS

AccS S

S

SS S

S

S

bullBreakage of crosslinks

bullRearrangement Cyclisation

bullShortening of crosslinks

bullIsomerisation conjugated double bonds

bullNew crosslinks

SSSS

Reversion process

SS

SS

SxS

S

SS S

SxSy-ACC

type of sulfur bridge bonding energy (kJmol)- C - SX - C - (x gt 2) lt 268- C - S2 - C - 268- C - S - C - 285- C - C - 352

Figure 3 Crosslink Bonding Energy

Torq

ueS

lsquo [s

tand

ardi

zed]

07

08

09

10

0 50 100 150

VSL 5025-0 (SSBR)

VSL 2525-0 (SSBR)

CB 24 (BR)

Natsyn 2200

NR (Crepe)

SL 25-0 (SSBR)

160degC

Figure 4 Influence of polymer on reversion

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Figure 1 Sulfur Crosslinking of Polyisoprene

Sulfur Crosslinks Form at the Allylic Hydrogen Atoms

Figure 2 Changes in network structure during reversion

S

SS

SS

S

SS

S

AccS

S SSSS

S

S

AccS

S

S

SSSS

AccS S

S

SS S

S

S

bullBreakage of crosslinks

bullRearrangement Cyclisation

bullShortening of crosslinks

bullIsomerisation conjugated double bonds

bullNew crosslinks

SSSS

Reversion process

SS

SS

SxS

S

SS S

SxSy-ACC

type of sulfur bridge bonding energy (kJmol)- C - SX - C - (x gt 2) lt 268- C - S2 - C - 268- C - S - C - 285- C - C - 352

Figure 3 Crosslink Bonding Energy

Torq

ueS

lsquo [s

tand

ardi

zed]

07

08

09

10

0 50 100 150

VSL 5025-0 (SSBR)

VSL 2525-0 (SSBR)

CB 24 (BR)

Natsyn 2200

NR (Crepe)

SL 25-0 (SSBR)

160degC

Figure 4 Influence of polymer on reversion

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Figure 2 Changes in network structure during reversion

S

SS

SS

S

SS

S

AccS

S SSSS

S

S

AccS

S

S

SSSS

AccS S

S

SS S

S

S

bullBreakage of crosslinks

bullRearrangement Cyclisation

bullShortening of crosslinks

bullIsomerisation conjugated double bonds

bullNew crosslinks

SSSS

Reversion process

SS

SS

SxS

S

SS S

SxSy-ACC

type of sulfur bridge bonding energy (kJmol)- C - SX - C - (x gt 2) lt 268- C - S2 - C - 268- C - S - C - 285- C - C - 352

Figure 3 Crosslink Bonding Energy

Torq

ueS

lsquo [s

tand

ardi

zed]

07

08

09

10

0 50 100 150

VSL 5025-0 (SSBR)

VSL 2525-0 (SSBR)

CB 24 (BR)

Natsyn 2200

NR (Crepe)

SL 25-0 (SSBR)

160degC

Figure 4 Influence of polymer on reversion

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

SS

SS

SxS

S

SS S

SxSy-ACC

type of sulfur bridge bonding energy (kJmol)- C - SX - C - (x gt 2) lt 268- C - S2 - C - 268- C - S - C - 285- C - C - 352

Figure 3 Crosslink Bonding Energy

Torq

ueS

lsquo [s

tand

ardi

zed]

07

08

09

10

0 50 100 150

VSL 5025-0 (SSBR)

VSL 2525-0 (SSBR)

CB 24 (BR)

Natsyn 2200

NR (Crepe)

SL 25-0 (SSBR)

160degC

Figure 4 Influence of polymer on reversion

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Torq

ueS

lsquo [s

tand

ardi

zed]

07

08

09

10

0 50 100 150

VSL 5025-0 (SSBR)

VSL 2525-0 (SSBR)

CB 24 (BR)

Natsyn 2200

NR (Crepe)

SL 25-0 (SSBR)

160degC

Figure 4 Influence of polymer on reversion

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Figure 5 Structure of Perkalinkreg900

N

O

O

N

O

O

13-Bis(citraconimidomethyl)benzenePerkalinkreg 900 (CIMB)

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism

N

O

O

N

O

O

+ +

N

O

O

N

O

O

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Figure 7 Distribution of Crosslinks in Vulcanizates+

CompoundCureConditions

Total CrosslinksX 105

PolysulfidicCrosslinksX 105

Di SulfidicCrosslinksX 105

Mono SulfidicX 105

Carbon-CarbonX 105

Control150deg Ct90 502 318 187 - -

170deg C30rsquo205 004 006 193 -

Perkalinkreg 900 15 phr

150deg Ct90 504 294 210 - -

170deg C30rsquo254 003 010 088 153

Concentration of Crosslinks gram-molegram hydrocarbon

+ ldquoA New Concept for Reversion Protection of Accelerated Sulfur Systemsrdquo

Presented at The ACS Rubber Division Meeting October 1994 Authors

RN Datta amp MS Ivany

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Figure 8 High Level Natural Rubber Compound

NR 80 phr BR 20 phr carbon black N539 40 phr silica 80 phr oil 30 phr IPPD 18 phr TMQ 12 phr ZnO RS 100 phr stearic acid 075 phr resin 20 phr

Cohedurreg RS (resorcinolstearic acid 21) 12 phr HMT 06 phr

Vulcanization system with Perkalink

CBS 07 07MBTS 03 03Sulfur 3 3CIMB 0 1

Reference

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

min

Figure 9 Rheometer (MDR 2000E 180degC)

reference

reference + 10 phr CIMB

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Diagramm1

Control
Control+10 CIMB
0
082
164
237
14
216
135
211
143
223
169
253
232
311
374
412
589
559
806
741
982
926
1119
1086
1231
1219
1321
1328
1394
1418
1458
1495
1509
1562
1552
1618
159
1666
1622
1707
1649
1742
1672
1773
1691
1799
1708
1822
1722
1841
1735
1858
1743
1871
175
1884
1757
1895
176
1902
1765
1909
1767
1915
1768
1919
1768
1923
1768
1924
1766
1926
1764
1927
1762
1928
1759
1926
1756
1925
1752
1923
1748
192
1744
1919
1739
1916
1733
1912
1727
1909
1723
1905
1717
19
171
1898
1704
1893
1698
1889
1693
1885
1685
188
168
1874
1672
187
1666
1864
1658
1859
1652
1854
1646
1849
1639
1844
1631
1839
1625
1834
1618
1829
1611
1823
1604
1817
1598
1813
1592
1808
1585
1803
1579
1798
1574
1793
1567
1788
1561
1783
1555
1778
1549
1773
1544
1768
1539
1764
1533
176
1527
1755
1523
1751
1517
1747
1513
1743
1507
1738
1501
1734
1496
1731
1494
1727
1488
1723
1484
172
1479
1716
1475
1712
147
1708
1465
1706
146
1702
1456
1698
1452
1696
1447
1692
1444
169
144
1687
1437
1683
1432
1681
1429
1678
1425
1675
1421
1672
1416
1669
1414
1667
141
1663
1406
1661
1402
1659
1399
1657
1395
1654
1392
1652
1389
1649
1386
1647
1383
1645
138
1644
1376
164
1374
1638
137
1637
1366
1634
1364
1633
136
1631
1358
1628
1354
1627
1351
1626
1349
1623
1346
1622
1343
1619
1341
1618
1337
1616
1335
1614
1332
1613
133
1611
1327
1609
1325
1607
1322
1607
132
1604
1316
1604
1314
1602
1312
1601
131
1599
1307
1599
1305
1597
1303
1596
1301
1596
1297
1594
1295
1593
1293
1591
1292
159
1291
1589
1287
1588
1286
1586
1283
1587
1282
1585
128
1584
1278
1583
1275
1582
1274
1581
1272
158
127
1579
1267
1577
1266
1577
1263
1576
1262
1575
126
1575
1257
1573
1257
1572
1255
1572
1253
1571
1251
157
125
157
1248
1569
1246
1568
1245
1568
1244
1567
1243
1566
1241
1566
124
1565
1238
1564
1237
1564
1235
1563
1233
1563
1231
1562
1231
1561
1228
1561
1228
1561
1226
1559
1225
1559
1223
1558
1222
1557
122
1558
1219
1557
1218
1556
1217
1557
1215
1556
1214
1555
1212
1556
1211
1554
121
1554
1208
1554
1207
1553
1206
1553
1205
1553
1203
1552
1203
1552
1201
1552
12
1551
12
1551
1199
1551
1196
1551
1196
1549
1195
155
1194
1549
1192
1549
1192
1549
119
1548
119
1548
1189
1548
1188
1548
1187
1548
1187
1548
1186
1547
1185
1547
1183
1547
1183
1547
1181
1547
118
1546
118
1546
1179
1546
1178
1546
1177
1546
1176
1546
1176
1545
1175
1545
1174
1545
1173
1545
1172
1545
1171
1545
1171
1545
117
1545
1169
1545
1167
1545
1167
1545
1166
1545
1166
1545
1165
1545
1164
1545
1163
1545
1162
1545
1162
1545
1161
1545
116
1545
116
1545
1159
1545
1158
1545
1158
1545
1157
1545
1156
1544
1156
1544
1155
1545
1154
1545
1153
1545
1153
1544
1152
1545
1152
1545
1151
1543
1151
1545
115
1545
115
1544
1148
1545
1148
1545
1148
1544
1147
1545
1147
1545
1146
1544
1146
1545
1145
1545
1145
1544
1145
1544
1143
1545
1143
1545
1142
1545
1142
1545
1141
1545
114
1545
114
1545
114
1544
114
1545
1139
1545
1138
1545
1138
1545
1138
1545
1138
1545
1137
1545
1137
1545
1137
1545
1136
1545
1136
1545
1134
1546
1135
1545
1134
1545
1134
1545
1133
1545
1132
1546
1132
1545
1132
1545
1131
1546
1131
1546
1131
1546
1131
1546
113
1546
1129
1546
1129
1547
1129
1546
1128
1546
1128
1547
1127
1547
1128
1546
1127
1547
1127
1547
1126
1547
1126
1547
1126
1547
1125
1547
1125
1548
1125
1548
1124
1547
1124
1548
1123
1548
1123
1548
1123
1548
1123
1547
1122
1548
1122
1548
1122
1549
1121
1549
1122
1549
112
1549
112
1549
112
1549
1121
1549
112
1549
112
155
1119
155
1118
155
1118
155
1118
155
1118
1551
1118
1551
1117
155
1118
1552
1117
1551
1117
1551
1116
1552
1116
1552
1115
1552
1116
1553
1115
1552
1115
1552
1114
1553
1115
1553
1115
1553
1114
1553
1114
1553
1113
1553
1113
1554
1113
1553
1113
1554
1112
1554
1113
1555
1112
1554
1112
1554
1112
1555
1112
1554
1111
1555
1111
1555
111
1556
111
1556

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556
0 0
008 008
016 016
024 024
032 032
04 04
048 048
056 056
064 064
072 072
08 08
088 088
096 096
104 104
112 112
12 12
128 128
136 136
144 144
152 152
16 16
168 168
176 176
184 184
192 192
2 2
208 208
216 216
224 224
232 232
24 24
248 248
256 256
264 264
272 272
28 28
288 288
296 296
304 304
312 312
32 32
328 328
336 336
344 344
352 352
36 36
368 368
376 376
384 384
392 392
4 4
408 408
416 416
424 424
432 432
44 44
448 448
456 456
464 464
472 472
48 48
488 488
496 496
504 504
512 512
52 52
528 528
536 536
544 544
552 552
56 56
568 568
576 576
584 584
592 592
6 6
608 608
616 616
624 624
632 632
64 64
648 648
656 656
664 664
672 672
68 68
688 688
696 696
704 704
712 712
72 72
728 728
736 736
744 744
752 752
76 76
768 768
776 776
784 784
792 792
8 8
808 808
816 816
824 824
832 832
84 84
848 848
856 856
864 864
872 872
88 88
888 888
896 896
904 904
912 912
92 92
928 928
936 936
944 944
952 952
96 96
968 968
976 976
984 984
992 992
10 10
1008 1008
1016 1016
1024 1024
1032 1032
104 104
1048 1048
1056 1056
1064 1064
1072 1072
108 108
1088 1088
1096 1096
1104 1104
1112 1112
112 112
1128 1128
1136 1136
1144 1144
1152 1152
116 116
1168 1168
1176 1176
1184 1184
1192 1192
12 12
1208 1208
1216 1216
1224 1224
1232 1232
124 124
1248 1248
1256 1256
1264 1264
1272 1272
128 128
1288 1288
1296 1296
1304 1304
1312 1312
132 132
1328 1328
1336 1336
1344 1344
1352 1352
136 136
1368 1368
1376 1376
1384 1384
1392 1392
14 14
1408 1408
1416 1416
1424 1424
1432 1432
144 144
1448 1448
1456 1456
1464 1464
1472 1472
148 148
1488 1488
1496 1496
1504 1504
1512 1512
152 152
1528 1528
1536 1536
1544 1544
1552 1552
156 156
1568 1568
1576 1576
1584 1584
1592 1592
16 16
1608 1608
1616 1616
1624 1624
1632 1632
164 164
1648 1648
1656 1656
1664 1664
1672 1672
168 168
1688 1688
1696 1696
1704 1704
1712 1712
172 172
1728 1728
1736 1736
1744 1744
1752 1752
176 176
1768 1768
1776 1776
1784 1784
1792 1792
18 18
1808 1808
1816 1816
1824 1824
1832 1832
184 184
1848 1848
1856 1856
1864 1864
1872 1872
188 188
1888 1888
1896 1896
1904 1904
1912 1912
192 192
1928 1928
1936 1936
1944 1944
1952 1952
196 196
1968 1968
1976 1976
1984 1984
1992 1992
20 20
2008 2008
2016 2016
2024 2024
2032 2032
204 204
2048 2048
2056 2056
2064 2064
2072 2072
208 208
2088 2088
2096 2096
2104 2104
2112 2112
212 212
2128 2128
2136 2136
2144 2144
2152 2152
216 216
2168 2168
2176 2176
2184 2184
2192 2192
22 22
2208 2208
2216 2216
2224 2224
2232 2232
224 224
2248 2248
2256 2256
2264 2264
2272 2272
228 228
2288 2288
2296 2296
2304 2304
2312 2312
232 232
2328 2328
2336 2336
2344 2344
2352 2352
236 236
2368 2368
2376 2376
2384 2384
2392 2392
24 24
2408 2408
2416 2416
2424 2424
2432 2432
244 244
2448 2448
2456 2456
2464 2464
2472 2472
248 248
2488 2488
2496 2496
2504 2504
2512 2512
252 252
2528 2528
2536 2536
2544 2544
2552 2552
256 256
2568 2568
2576 2576
2584 2584
2592 2592
26 26
2608 2608
2616 2616
2624 2624
2632 2632
264 264
2648 2648
2656 2656
2664 2664
2672 2672
268 268
2688 2688
2696 2696
2704 2704
2712 2712
272 272
2728 2728
2736 2736
2744 2744
2752 2752
276 276
2768 2768
2776 2776
2784 2784
2792 2792
28 28
2808 2808
2816 2816
2824 2824
2832 2832
284 284
2848 2848
2856 2856
2864 2864
2872 2872
288 288
2888 2888
2896 2896
2904 2904
2912 2912
292 292
2928 2928
2936 2936
2944 2944
2952 2952
296 296
2968 2968
2976 2976
2984 2984
2992 2992
30 30

Sheet1

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
Control Control+10 CIMB
0 0 082
008 164 237
016 14 216
024 135 211
032 143 223
04 169 253
048 232 311
056 374 412
064 589 559
072 806 741
08 982 926
088 1119 1086
096 1231 1219
104 1321 1328
112 1394 1418
12 1458 1495
128 1509 1562
136 1552 1618
144 159 1666
152 1622 1707
16 1649 1742
168 1672 1773
176 1691 1799
184 1708 1822
192 1722 1841
2 1735 1858
208 1743 1871
216 175 1884
224 1757 1895
232 176 1902
24 1765 1909
248 1767 1915
256 1768 1919
264 1768 1923
272 1768 1924
28 1766 1926
288 1764 1927
296 1762 1928
304 1759 1926
312 1756 1925
32 1752 1923
328 1748 192
336 1744 1919
344 1739 1916
352 1733 1912
36 1727 1909
368 1723 1905
376 1717 19
384 171 1898
392 1704 1893
4 1698 1889
408 1693 1885
416 1685 188
424 168 1874
432 1672 187
44 1666 1864
448 1658 1859
456 1652 1854
464 1646 1849
472 1639 1844
48 1631 1839
488 1625 1834
496 1618 1829
504 1611 1823
512 1604 1817
52 1598 1813
528 1592 1808
536 1585 1803
544 1579 1798
552 1574 1793
56 1567 1788
568 1561 1783
576 1555 1778
584 1549 1773
592 1544 1768
6 1539 1764
608 1533 176
616 1527 1755
624 1523 1751
632 1517 1747
64 1513 1743
648 1507 1738
656 1501 1734
664 1496 1731
672 1494 1727
68 1488 1723
688 1484 172
696 1479 1716
704 1475 1712
712 147 1708
72 1465 1706
728 146 1702
736 1456 1698
744 1452 1696
752 1447 1692
76 1444 169
768 144 1687
776 1437 1683
784 1432 1681
792 1429 1678
8 1425 1675
808 1421 1672
816 1416 1669
824 1414 1667
832 141 1663
84 1406 1661
848 1402 1659
856 1399 1657
864 1395 1654
872 1392 1652
88 1389 1649
888 1386 1647
896 1383 1645
904 138 1644
912 1376 164
92 1374 1638
928 137 1637
936 1366 1634
944 1364 1633
952 136 1631
96 1358 1628
968 1354 1627
976 1351 1626
984 1349 1623
992 1346 1622
10 1343 1619
1008 1341 1618
1016 1337 1616
1024 1335 1614
1032 1332 1613
104 133 1611
1048 1327 1609
1056 1325 1607
1064 1322 1607
1072 132 1604
108 1316 1604
1088 1314 1602
1096 1312 1601
1104 131 1599
1112 1307 1599
112 1305 1597
1128 1303 1596
1136 1301 1596
1144 1297 1594
1152 1295 1593
116 1293 1591
1168 1292 159
1176 1291 1589
1184 1287 1588
1192 1286 1586
12 1283 1587
1208 1282 1585
1216 128 1584
1224 1278 1583
1232 1275 1582
124 1274 1581
1248 1272 158
1256 127 1579
1264 1267 1577
1272 1266 1577
128 1263 1576
1288 1262 1575
1296 126 1575
1304 1257 1573
1312 1257 1572
132 1255 1572
1328 1253 1571
1336 1251 157
1344 125 157
1352 1248 1569
136 1246 1568
1368 1245 1568
1376 1244 1567
1384 1243 1566
1392 1241 1566
14 124 1565
1408 1238 1564
1416 1237 1564
1424 1235 1563
1432 1233 1563
144 1231 1562
1448 1231 1561
1456 1228 1561
1464 1228 1561
1472 1226 1559
148 1225 1559
1488 1223 1558
1496 1222 1557
1504 122 1558
1512 1219 1557
152 1218 1556
1528 1217 1557
1536 1215 1556
1544 1214 1555
1552 1212 1556
156 1211 1554
1568 121 1554
1576 1208 1554
1584 1207 1553
1592 1206 1553
16 1205 1553
1608 1203 1552
1616 1203 1552
1624 1201 1552
1632 12 1551
164 12 1551
1648 1199 1551
1656 1196 1551
1664 1196 1549
1672 1195 155
168 1194 1549
1688 1192 1549
1696 1192 1549
1704 119 1548
1712 119 1548
172 1189 1548
1728 1188 1548
1736 1187 1548
1744 1187 1548
1752 1186 1547
176 1185 1547
1768 1183 1547
1776 1183 1547
1784 1181 1547
1792 118 1546
18 118 1546
1808 1179 1546
1816 1178 1546
1824 1177 1546
1832 1176 1546
184 1176 1545
1848 1175 1545
1856 1174 1545
1864 1173 1545
1872 1172 1545
188 1171 1545
1888 1171 1545
1896 117 1545
1904 1169 1545
1912 1167 1545
192 1167 1545
1928 1166 1545
1936 1166 1545
1944 1165 1545
1952 1164 1545
196 1163 1545
1968 1162 1545
1976 1162 1545
1984 1161 1545
1992 116 1545
20 116 1545
2008 1159 1545
2016 1158 1545
2024 1158 1545
2032 1157 1545
204 1156 1544
2048 1156 1544
2056 1155 1545
2064 1154 1545
2072 1153 1545
208 1153 1544
2088 1152 1545
2096 1152 1545
2104 1151 1543
2112 1151 1545
212 115 1545
2128 115 1544
2136 1148 1545
2144 1148 1545
2152 1148 1544
216 1147 1545
2168 1147 1545
2176 1146 1544
2184 1146 1545
2192 1145 1545
22 1145 1544
2208 1145 1544
2216 1143 1545
2224 1143 1545
2232 1142 1545
224 1142 1545
2248 1141 1545
2256 114 1545
2264 114 1545
2272 114 1544
228 114 1545
2288 1139 1545
2296 1138 1545
2304 1138 1545
2312 1138 1545
232 1138 1545
2328 1137 1545
2336 1137 1545
2344 1137 1545
2352 1136 1545
236 1136 1545
2368 1134 1546
2376 1135 1545
2384 1134 1545
2392 1134 1545
24 1133 1545
2408 1132 1546
2416 1132 1545
2424 1132 1545
2432 1131 1546
244 1131 1546
2448 1131 1546
2456 1131 1546
2464 113 1546
2472 1129 1546
248 1129 1547
2488 1129 1546
2496 1128 1546
2504 1128 1547
2512 1127 1547
252 1128 1546
2528 1127 1547
2536 1127 1547
2544 1126 1547
2552 1126 1547
256 1126 1547
2568 1125 1547
2576 1125 1548
2584 1125 1548
2592 1124 1547
26 1124 1548
2608 1123 1548
2616 1123 1548
2624 1123 1548
2632 1123 1547
264 1122 1548
2648 1122 1548
2656 1122 1549
2664 1121 1549
2672 1122 1549
268 112 1549
2688 112 1549
2696 112 1549
2704 1121 1549
2712 112 1549
272 112 155
2728 1119 155
2736 1118 155
2744 1118 155
2752 1118 155
276 1118 1551
2768 1118 1551
2776 1117 155
2784 1118 1552
2792 1117 1551
28 1117 1551
2808 1116 1552
2816 1116 1552
2824 1115 1552
2832 1116 1553
284 1115 1552
2848 1115 1552
2856 1114 1553
2864 1115 1553
2872 1115 1553
288 1114 1553
2888 1114 1553
2896 1113 1553
2904 1113 1554
2912 1113 1553
292 1113 1554
2928 1112 1554
2936 1113 1555
2944 1112 1554
2952 1112 1554
296 1112 1555
2968 1112 1554
2976 1111 1555
2984 1111 1555
2992 111 1556
30 111 1556

reference reference + 10 CIMB

Figure 10 300 Modulus

MPa

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB

Diagramm1

t95 150degC
120min 160degC
124
79
129
108

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB

Sheet1

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 124 129
120min 160degC 79 108

Figure 11 Tangent Delta 70degC

tan δ

7

0degC

(Roelig DIN 53513 10Hz)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB

Diagramm1

t95 150degC
120min 160degC
0043
0099
0049
0073

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB

Sheet1

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB
reference (30 S) reference +10 CIMB
t95 150degC 0043 0049
120min 160degC 0099 0073

Figure 12 Goodrich Flexometer - HBU

(100degC25 min pre strain 1MPa deformation 445 mm)

Reference Reference + 10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB

Diagramm1

t95 150degC
120min 160degC
109
192
109
139

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139
reference (30 S) reference (30 S)
reference +10 CIMB reference +10 CIMB

Sheet1

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren
reference (30 S) reference +10 CIMB
t95 150degC 109 109
120min 160degC 192 139

Summary Part 1

- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)

- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion

- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren

Part II Figure 13 Vulcurenreg Structure

16-Bis(NN-dibenzylthiocarbamolydithio)hexane(BDzTH)

S

SN

S(CH2)6

S

SN

S

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren

Figure 14 Crosslink Formed During Vulcanization

S

S

S

S

SS

S

Acc

S

SS

S S

S

Stable network from the beginning and retaining flexibility

6(CH )sup2 S x CHsup2

S xCHsup2

Hybrid Crosslinks with x le 3

Carbasulfane Crosslink

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren

0

000002

000004

000006

000008

00001

000012

000014

t95 150degC 120 min 160degC t95 150degC 120 min 160degC

Crossl

ink De

nsity

molcm

sup3

-S-C6H12-S- Sx S2 S1

Figure 15 Distribution of crosslink structures before and after heat ageing

Σ 121 x 10-5 molcmsup3

Σ 91 x 10-5 molcmsup3

Σ 116 x 10-5 molcmsup3 Σ 120x 10-5 molcmsup3

15 phr S 15 phr CBS 25 phr BDzTH 05 phr S 15 phr CBS

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren

Figure 16 Recipe ndash Truck tread

conventional semi EV VulcurenregSMR 5 premasticated 100 100 100

Stearic Acid 1 1 1Zinc Oxide 5 5 5

Carbon black N375 50 50 50Aromatic Oil 3 3 3Antiluxreg 654 1 1 1

Vulkanoxreg 4020 (6PPD) 2 2 2Vulkanoxreg HS (TMQ) 1 1 1

Vulkacitreg CZ (CBS) 05 15 15Sulfur 25 15 05

Vulcurenreg 0 0 25

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren

Figure 17 Rheometer ndash NR truck tread

MDR 2000E 180degC

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren

Figure 18 Tensile Strength

T95 150degC

120 min160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren

Diagramm1

t95 bei 150degC
120 min bei 160degC
MPa
292
146
313
22
298
275

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275
conv conv
semi EV semi EV
Vulcuren Vulcuren

Sheet1

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV TESPT Vulcuren
t95 bei 150degC 292 313 30 298
120 min bei 160degC 146 22 247 275

Figure 19 Residual Tensile Strength

0

20

40

60

80

100

conv semi EV Vulcuren

[]

t95 bei 150degC 7d Heiszligluftalterung bei 100degCt95 150degC 7 Days Oven Aged at 100degC

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren

Diagramm1

t95 bei 150degC
7d Heiszligluftalterung bei 100degC
[]
100
284
100
466
100
725

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725
conv conv
semi EV semi EV
Vulcuren Vulcuren

Tabelle1

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren
conv semi EV Vulcuren
100 100 100
284 466 725

Tabelle1

t95 bei 150degC
7d Heisluftalterung bei 100degC
residuale tensile stregth []

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren

Tabelle2

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren

Tabelle3

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren

Figure 20 Goodrich Flexometer - HBU

100degC25 min pre strain 1MPa Deformation 445 mm

Tem

pera

ture

rise∆Τ

degC

T95 150degC 120 min 160degC

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren

Diagramm1

t95 bei 150degC
120 min bei 160degC
339
449
178
324
198
219

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219
conv conv
semi EV semi EV
Vulcuren Vulcuren

Sheet1

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
conv semi EV TESPT Vulcuren
t95 bei 150degC 339 178 188 198
120 min bei 160degC 449 324 23 219

0

2

4

6

8

10

12

14

16

18

20

0 5 10 15 20 25 30

Time [min]

Torq

ue [d

Nm]

Control A Vulcuren B

Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound

E-SBR BR N234 Carbon Black Vulcuren 1 phr

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43

Figure 22 Truck Tire TestKRAIBURG Tread K52-250

Cure systems

Control Vulcurenreg

TBBS 18 12

MBTS 02 02

Sulfur 15 08

Vulcurenreg - 20

NRSBRBR-blend50 phr carbon black

The vulcanizate properties of the unaged tread compound with Vulcurenreg wereadjusted to the level of the control

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43

Figure 23 Truck Tire Test

Vulcanizate properties of unaged compounds

Cure systemsControl Vulcurenreg

Tensile Strength Mpa 23 22Elongation at break 495 456100 Modulus Mpa 22 23300 Modulus Mpa 111 119Hardness Shore A 65 67Elasticity 46 48Tear Resistance Nmm 42 35

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43

Figure 24 Truck Tire Test Vehicle

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43

Figure 25 Truck Tire TestScope and conditions

Truck Tires 31570 R 225 Traction Axle

Kraiburg Tread K 52-250 ( modified Michelin XDE 2 tread pattern) based on a compound with a SBRBRNR - blendA cure system with Vulcurenreg was compared to the standard cure system

The tires were used on trucks in long distance traffic

Vulcurenreg

VulcurenregStandard

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 1

VulcurenTruck 1

Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 2

VulcurenTruck 2

Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 3

VulcurenTruck 3

Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43

810121416182022

0 20000 40000 60000 80000 100000

Prof

ile d

epth

[mm

]

Test distance [km]

StdTruck 4

VulcurenTruck 4

Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)

Vulcuren

Standard

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43

Summary Part II

- Vulcurenreg provides a unique type of carbasulfane-crosslink

- The reversion resistance of NR vulcanizates can be significantlyimproved by the use of Vulcurenreg

- Vulcurenreg also reduces reversion in compounds based on synthetic rubber

- A truck field test showed about 10 better abrasion resistance with the addition of Vulcurenreg

In summary Vulcurenreg offers significant possibilities to improve the performance of rubber products

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43

Conclusion

- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber

- Reducing reversion can add significant service life to large expensive tires that designed for severe service

- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required

  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43
  • Slide Number 1
  • Slide Number 2
  • Slide Number 3
  • Slide Number 4
  • Slide Number 5
  • Slide Number 6
  • Slide Number 7
  • Properties of Crosslink Structure
  • Figure 1 Sulfur Crosslinking of Polyisoprene
  • Figure 2 Changes in network structure during reversion
  • Figure 3 Crosslink Bonding Energy
  • Figure 4 Influence of polymer on reversion
  • Figure 5 Structure of Perkalinkreg900
  • Figure 6 CIMB Crosslink Formation- Diels-Alder Mechanism
  • Figure 7 Distribution of Crosslinks in Vulcanizates+
  • Figure 8 High Level Natural Rubber Compound
  • Figure 9 Rheometer (MDR 2000E 180degC)
  • Figure 10 300 Modulus
  • Figure 11 Tangent Delta 70degC
  • Figure 12 Goodrich Flexometer - HBU
  • Summary Part 1- Perkalinkreg 900 becomes active when the rubber compound is exposed to excessive heat (beyond optimum cure time and temperature or heat generated in service)- Perkalinkreg 900 forms strong flexible carbon-carbon crosslinks that replace weaker polysulfidic crosslinks which are prone to break and shorten causing reversion- Rubber compounds containing Perkalinkreg 900 exhibit superior retention of physical properties after heat aging
  • Part II Figure 13 Vulcurenreg Structure
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 14 Crosslink Formed During Vulcanization
  • Figure 15 Distribution of crosslink structures before and after heat ageing
  • Figure 16 Recipe ndash Truck tread
  • Figure 17 Rheometer ndash NR truck tread
  • Figure 18 Tensile Strength
  • Figure 19 Residual Tensile Strength
  • Figure 20 Goodrich Flexometer - HBU
  • Figure 21 Rheometer MDR 2000E 170degCConventional Synthetic Rubber Tread Compound
  • Figure 22 Truck Tire TestKRAIBURG Tread K52-250
  • Figure 23 Truck Tire Test
  • Figure 24 Truck Tire Test Vehicle
  • Figure 25 Truck Tire TestScope and conditions
  • Figure 26 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 27 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 28 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Figure 29 Decrease of profile depthTruck Tire Road Test (31570 R 225 Traction Axle)
  • Summary Part II- Vulcurenreg provides a unique type of carbasulfane-crosslink- The reversion resistance of NR vulcanizates can be significantly improved by the use of Vulcurenreg- Vulcurenreg also reduces reversion in compounds based on synthetic rubber- A truck field test showed about 10 better abrasion resistance with the addition of VulcurenregIn summary Vulcurenreg offers significant possibilities to improve the performance of rubber products
  • Conclusion- Perkalinkreg 900 and Vulcurenreg each provide a unique method of reducing reversion in rubber compounds particularly compounds containing high levels of natural rubber- Reducing reversion can add significant service life to large expensive tires that designed for severe service- These additives offer the Tire Compounder a choice when the need to reduce compound reversion is required
  • Slide Number 42
  • Slide Number 43