[email protected] … · john florio z. a. he ed ... jason poff contributors to this work....
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Catalysis of IsocyanatesWerner J. Blank
SL2195
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Mike Emmet John FlorioZ. A. He Ed HessellMarie E. PicciMike ThomasJason Poff
Contributors to this Work
CATALYSIS OF ISOCYANATES
HYDROXYL-ISOCYANATE REACTIONDIFFERENT CATALYSTS DBTDL, Al, Bi, ZrHOW TO SELECT A CATALYSTREACTION RATES WITH HYDROXYLSELECTIVITY OF OH vs WATERFORMULATION GUIDE LINES
BLOCKED ISOCYANATES
ISOCYANATE REACTIONS
R-OH
R-COOHR-NHCONH-RR-NHCOO-R
TRIMERDIMER
EPOXYR-NH2
HOH
CARBODIIMIDE
R-NCO
SL2196R-CH2 act.
CATALYSIS PROBLEMS
HIGH SOLIDS COATINGS
POTLIFE/REACTIVITYMOISTURE REACTIONSOLUBILITYNETWORK STABILITY
WATERBORNE
WATER REACTIONPOTLIFEGASSINGSTABILITYGLOSS
Objectives of this Study
ENVIRONMETALLY ACCEPTABLE CATALYSTS
REACTION RATE OF CATALYSTS WITH OH
SELECTIVE CATALYSTS FOR OH
IMPROVED POTLIFE/REACTIVITY
REDUCED WATER REACTION
CATALYSTS USED
DIBUTYLTIN DILAURATE / DIACETATEDIBUTYLTIN OXIDE MERCURY COMPOUNDS LEAD COMPOUNDSAMINESZINC SALTSMANGANESE SALTS
CATALYST PROPERTIESPOTLIFE / REACTIVITYSELECTIVITYDELAYED ACTIONLOW TEMPERATUREHIGH TEMPERATUREWATERHIGH RATE (RIM)EXTERIOR DURABILITYRESISTANCE PROPERTIESENVIRONMENT - TOXICITY
SL2197
Isocyanate-Hydroxyl Reactions
ROH + R’NCO R’NHCOOR
CO CO 22
R’NH +2 R’NCO R’NHCONHR’
R’NCO + H2 O R’-NHCOOH R’-NH2
SL2198
SCREENING OF CATALYSTS
APPLICATION TESTS FORMULATIONPOTLIFE (2X VISC.)GEL TIMETACK FREEDRY-THROUGH
MODEL SYSTEMS (ANALYTICAL)DISAPPEARANCE OF NCOFORMATION OF URETHANE / UREAMW
0
60
120
180
240
300
360
420
480
540
600
Visc
osity
(min
@ 2
5°C
)
0
5
10
15
20
25
30
Tack
Fre
e (h
rs @
25°
C)
A B C D E F G H I J K L M N O P Q
Catalyst
VISC. 2X Tack Free (hrs)
Catalyst Study (HDI TRIMER)Metal (0.0065% on Solids)
A: DBTDLB: DBTDAC: Mn Naph/PDD: Mn OctE: Sn Oct/PDF: Vn acac/PDG: Vn acacH: Bi OctI: Bi NaphJ: Zn acac/PDK: Zn OctL: Co OctM: Zr acacN: Zr acac/PDO: Zr OctP: Al acacQ:Al chelate/PD
SL2242
150
200
250
300
350
400
Visc
osity
(cps
)
90
92
94
96
98
100
Unr
eact
ed N
CO
0 100 200 300 400 500 600 Minutes @ 25°C
% NCO VISCOSITY
PE/HDI-TRIMERNo Catalyst
SL2017
1E0
1E1
1E2
1E3
1E4
TIM
E. m
inut
e
0.0001 0.001 0.01 0.1 DBTDL, Sn %
Potlife TACK FREE
PE/HDI-TRIMERCATALYST REACTION RATE
SL2245
NETWORK FORMATIONA4 + B2
0
2
4
6
8
10
0 0.2 0.4 0.6 0.8 1
CONVERSION
DE
GR
EE
OF
P
OL
YM
ER
IZA
TIO
N
00.20.40.60.811.21.41.61.82
FR
AC
TIO
N
Mw
Mn
Ws
P(X3)
P(X4)
CATALYSTS
Zr ChA……….XC-4205…….ZrAcAcZr ChB……….XC-6212…….Zr DionateAl Ch1………..XC-5218…….Al DionateBi carb……….K-348………..Bi Oct.DBTDL………………………..Dibutyltin C12DBTDA……………………….Dibutyltin Ac
23482308
22682228
2940 2460 1980 1500 1020 5
39 58.5
0.00
0.10
0.20
0.30
0.40
0.50
0.60
Ab
s
Wavenumber
Time (sec)
Isocyanate Peak Decay
REACTIVITY WITH DIFFERENT HYDROXYL GROUPS
OH
OH
OH
OOH
O
NH
OOH
O
OOH
OO
OHO
N-BUTANOL
ISOBUTANOL
2-BUTANOL
HEC
BUCELL
METRIPOP
HEE
HDI TRIMER / HYDROXYLDBTDL 0.0140% Sn
n-BUTANOL
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 1000 2000 3000 4000 5000 6000
TIME, sec
NC
O N
OR
MA
LIZE
D DBTDL 0.014 % Sn
Zr CHEL. 0.014 % Zr
Bi CARB. 0.014 % Bi
DABCO 1 %
Zn OCT. 0.014 % Zn
0
0.2
0.4
0.6
0.8
NC
O N
OR
MAL
IZED
300
0 se
c.
Bi Dabco DBTDL Zn Oct. Zr ChelCATALYST
n-BUTANOL
2BUCEL
HEE
HEC
HDI-TRIMER/HYROXYLPRIMARY HYDROXL
0.134 % 10% 0.0134 %
0.268 %
0.0134 %
SL2337
0
0.2
0.4
0.6
0.8
1
NC
O N
OR
MA
LIZE
D 3
000
sec.
Bi Dabco DBTDL Zn Oct. Zr ChelCATALYST
n-BUTANOL
2-BUTANOL
ISOBUTANOL
HDI-TRIMER/HYROXYLpri, sec BUTANOL
0.134 % 10% 0.0134 %
0.268 %
0.0134 %
SL2338
0
0.2
0.4
0.6
0.8
1
NC
O N
OR
MA
LIZE
D 3
000
sec.
Bi Dabco DBTDL Zn Oct. Zr ChelCATALYST
n-BUTANOL
2-BUTANOL
2-BUCELL
METRIPROP
HDI-TRIMER/HYROXYLpri, sec BUTANOL, ETHER
0.134 % 10% 0.0134 %
0.268 %
0.0134 %
SL2339
Polyether MDI Elastomer Bi Oct. 1/5 mol WATER
0
50000
100000
150000
200000
250000
0 20 40 60 80 100
Time, minutes
Vis
cosi
ty, c
P
Bi Oct. Initial Bi Oct. 2 days Bi Oct. 7 days
CATALYSTS
Zr ChA……….XC-4205…….ZrAcAcZr ChB……….XC-6212…….Zr Dionate
XC-9213…….Zr DionateAl Ch1………..XC-5218…….Al DionateBi carb……….K-348………..Bi Oct.Bi carb……….XC-8203...…..Bi Carb.DBTDL………………………..Dibutyltin C12DBTDA………………………..Dibutyltin Ac
0
50
100
150
200 G
EL T
IME
(min
)
0 0.01 0.02 0.03 CATALYST CONCENTRATION (Me, %)
Zr B Zr A DBTDL
GEL TIMEACRYLIC/HDI-TIMER
SL2073
0
50
100
150
200
250
300 Ti
me
(min
.)
0 0.005 0.01 0.015 0.02 CATALYST CONC. Me %
Zr B Zr A DBTDL
Tack Free time Acrylic HDI-Trimer
SL2077
0
100
200
300
400
Tim
e ( m
in.)
0 0.005 0.01 0.015 0.02 CATALYST, CONC Me %
Zr B Zr A DBTDL
DRY THROUGH TIMEACRYLIC/HDI-TRIMER, 30 µ,RT, 66 % RH
SL2075
1900.0 1800 1700 1600 1500 1400
1/CM
A
urea
urethane
urethane + urea
1698
1698
1647
1647
1568
1461
1539
1570
1462
1461
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6 A
BSO
RB
AN
CE
1500 1600 1700 1800 WAVENUMBER CM-1
ZIRC A DBTDL
SELECTIVITY OF CATALYSISDBTDL & Zr CHELATE
UREA
SL2183
1900.0 1800 1700 1600 1500 1400.0
1/cm
A
urea
urethane
Zr diketonate
DBTDL
Zn octoate
urea
urethane
/
\
\
/
0 1 2 3 4 5 6 7 RELATIVE SELECTIVITY URETH/UREA
XC-6212
Uncatalyzed
DBTDL
K-5218
DBTDAC
K-348
Zn oct
Co octC
ATA
LYST
SELECTIVITY HYDROXYL / WATER
NCO/OH/WATER 1/1/2
0
20
40
60
80
100 W
EIG
HT,
%
Sn 0.0074% Zr 0.008 %
WATER
HDI-TRI
POLYMER
WATERBORNE TWO COMPONENT
SL2192
0
2
4
6
8
TIM
E, H
OU
RS
No catalyst DBTDL Zr CHCATALYST
TACK FREE THROUGH DRY
WATERBORNE TWO COMPONENT
SL2193
0
20
40
60
80
100 G
LOSS
, %
0
1
2
3
4
5
MA
XIM
UM
PO
TLIF
E, H
RS
No catalyst DBTDL Zr CHGLOSS 20° GLOSS 60° POTLIFE
WATERBORNE TWO COMPONENTCATALYST SELECTION
SL2194
LEWIS ACID CATALYSIS
R-N=C=O + R” SnX22
+ R’OH
R - N=C=O2R”
Sn
2X
-+
R -N=C=O2R”
Sn2X
-
O H R’+
R-NHCOOR’ + R” SnX 22SL2200
AMINE CATALYSIS
OR-N-C
O-R’H
+ R”3N
R”3N + H- O- R’ R”3N….H….O- R’
+
R”3N….H….O- R’ + R-N=C=O R-N….C….O
R”3N….H….O- R’
-
SL2201
3(AcAc) Zr-OR
4(AcAc) Zr 4(AcAc) Zr R
0H
+ROH
- ROH
-AcAc+AcAc(slow)
(fast)
ZIRCONIUM CHELATE CATALYSIS
SL2203
3(AcAc) Zr-OR R’-NCO
3(AcAc) Zr-OR
R’N=C=O
3
O ||
(AcAc) Zr-N-C-OR| R’
ROH
O||
R’NH-C-OR
ZIRCONIUM CHELATE CATALYSIS
SL2204
3(AcAc) ZrOH 3(AcAc) ZrOZr(AcAc)3
Zr(AcAc) + H O4 2 3
(AcAc) ZrOH+AcAc
HYDROLYSIS OF Zr CHELATE
SL2205
DELAYED ACTION OF Bi CARBOXYLATE
Bi (RCOO)3 + H2O Bi2O3 + RCOOH
Bi2O3 + RCOOH Bi (RCOO)3 + H2O
R-NHCOOH + Bi2O3 Bi (RNHCOO)3
DEACTIVATION
ACTIVATION
H2O + RNCO R-NHCOOH R-NH2 + C02
WHY REPLACE DBTDL
ENVIRONMENTAL Al, Bi, ZrPOTLIFE - REACTIVITY AlPIGMENT ABSORPTION AlSELECTIVITY - HYDROXYL vs WATER Zr
LOW GLOSS HIGH HUMIDITY ZrGASSING Zr
WATERBORNE ZrDELAYED REACTION BiSIDE REACTIONS ZrHYDROLYSIS OF ESTER GROUPS Al, Bi, ZrDURABILITY Al, Bi, Zr
FORMULATION GUIDE LINES
CATALYST INHIBITION - DEACTIVATIONPIGMENT ABSORPTIONWATERACID NUMBERAMINE
HIGH SOLIDSPOTLIFE - REACTIVITYSOLUBILITY
WATERBORNEGASING CATALYSTHYDROLYSIS
0.0001
0.001
0.01
0.1
1
10
K-KA
T %
ON
BIN
DER
0.0001 0.001 0.01 0.1 1 DBTDL % ON BINDER
K-348 XC-9213 XC-8203 XC-6212 K-4205, K-5218
K-KAT CATALYST CONCENTRATIONDBTDL REPLACEMENT LEVEL
ALL CATALYST LEVELSAS SUPPLIED
CATALYSTS FORMULATION GUIDELINE Zr Chelate XC-6212, XC-9213
Add to isocyanateZr Chelate 4205
Water free formulation low in acid number
Bismuth carboxylate K-348, XC-8203COOH beneficialLow water contentDehydrating agents
Al Chelate K-5218Low acid number, neutralizationLow water content2,4-pentanedione addition
12
13
14
15
16
17 IC
I VIS
CO
SITY
, 25°
C, P
oise
initialy 2 weeks
CONTROL XC-6212
STABILITY OF HDI-TRIMER 50°CK-KAT XC-6212 (4%)
SL2079
0 60
120 180 240 300 360 420 480 540 600
VISC
OSI
TY, 2
X (m
in @
25°
C)
1.8 1.23 0.58 02,4-PENTANEDIONE on SOLIDS, %
K-KAT 5218 DBTDL
POLYESTER/HDI-TRIMERTACK FREE TIME 3.0-4.0 HOURS
SL2021
K-KAT 5218 1.3 %DBTDL 0.023%
0
10
20
30
40
50
60
VISC
OSI
TY, m
inut
es
0
2
4
6
8
10
12
TAC
K F
REE
, hou
rs
4 376 748 13472,4 PENTANEDION/Zr mole ratio
2X visc (min) Tack Free (hrs)
POLYESTER/HDI-TRIMER CATALYSTCATALYST Me 0.0065% ON SOLIDS
SL2015F
HIGH REACTION SPEEDPLURAL COMPONENT GUN…………….POT LIFEHEAT CURE……………………...EXTERIOR DURABILITYHIGH HUMIDITY…………………..WATERBORNENCO BLOCKEDPU-PREPOLYMER………………..RIM
K-348 Bi K-4205 Zr K-6212 ZrK-5218 AlDBTDL
CATALYST SELECTION
SL2210
0 2 4 6 8
10 12 14
AC
ID N
UM
BER
0 2 4 8 13 18TIME (weeks)
DBTDAc CONTROL K-KAT XC-6212
K-Kat 4205 K-Kat 348 K-Kat 5218
Hydrolysis of polyesterin presence of catalyst (0.01%on TRS)
SL2072
SUMMARYORGANO TIN FREE COATINGS POSSIBLE
CHOICE OF CATALYST DEPENDS ON APPLICATION
Zr CHELATE CATALYSTS SELECTIVE FOR OH
HIGH REACTION RATES POSSIBLE
RELATIVE REACTIVITY OF HYDROXYLS DIFFERENT
CATALYSIS OF WATERBORNE COATINGS WITH Zr
POTLIFE - REACTIVITY Al
Bi CATALYST SIMILAR TO DBTDL
REACTION OF BLOCKED ISOCYANATE
RNHCOO-BL RNCO + BL
RNCO + R’OH RNHCO-OR’
RNHCO-BL + R’OH RNHCO-OR’+BL
k1
k2
k1
k2
k3
0 50 100 150 200
DBTDL
K-KAT 348
Phenol Pyrazol Oxime
Carbitol Caprolactam Uretdione
BLOCKED ISOCYANATE++++++++
++++++++++++++++
++++++++++++
++++++++++++
MEK + °C
0 50 100 150 200
MEK / °C
uretdione
caprolactam
carbitol
pyrazol
phenol
oxime
K-KAT 348 No Cat Temp, °C
BLOCKED ISOCYANATE