This article was downloaded by: [University of Waterloo]On: 10 October 2014, At: 06:51Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,UK

International Journal ofPolymeric Materials andPolymeric BiomaterialsPublication details, including instructions forauthors and subscription information:http://www.tandfonline.com/loi/gpom20

Plasticizer Extenders forPolyvinyl Chloride (PVC)Chlorinated Esters and EtherN. D. Ghatge a , S. S. Mahajan a & S. V. Vaidya a ba National Chemical Laboratory , Pune, 477008,Indiab Ion Exchange (India) Ltd. , M.I.D.C. Estate,Ambarnath, ThanaPublished online: 19 Dec 2006.

To cite this article: N. D. Ghatge , S. S. Mahajan & S. V. Vaidya (1983) PlasticizerExtenders for Polyvinyl Chloride (PVC) Chlorinated Esters and Ether, InternationalJournal of Polymeric Materials and Polymeric Biomaterials, 10:2, 131-140, DOI:10.1080/00914038308080264

To link to this article: http://dx.doi.org/10.1080/00914038308080264

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all theinformation (the “Content”) contained in the publications on our platform.However, Taylor & Francis, our agents, and our licensors make norepresentations or warranties whatsoever as to the accuracy, completeness,or suitability for any purpose of the Content. Any opinions and viewsexpressed in this publication are the opinions and views of the authors, andare not the views of or endorsed by Taylor & Francis. The accuracy of theContent should not be relied upon and should be independently verified withprimary sources of information. Taylor and Francis shall not be liable for anylosses, actions, claims, proceedings, demands, costs, expenses, damages,

and other liabilities whatsoever or howsoever caused arising directly orindirectly in connection with, in relation to or arising out of the use of theContent.

This article may be used for research, teaching, and private study purposes.Any substantial or systematic reproduction, redistribution, reselling, loan,sub-licensing, systematic supply, or distribution in any form to anyone isexpressly forbidden. Terms & Conditions of access and use can be found athttp://www.tandfonline.com/page/terms-and-conditions

Dow

nloa

ded

by [

Uni

vers

ity o

f W

ater

loo]

at 0

6:51

10

Oct

ober

201

4

Intern. J . Polymeric Muter., 1983, Vol. 10, pp. 131-140

@ 1983 Gordon and Breach Science Publishers, Inc. Printed in the United Kingdom

0091 -4037/83/1oO2- 01 31 $18.50/0

Plasticizer Extenders for Polyvinyl Chloride (PVC) Chlorinated Esters and Ethert

N. D. GHATGE, S. S. MAHAJAN and S. V. VAIDYAS National Chemical Laboratory, Pune-47 7008, India

(Received August 24, 1982)

The preparation of chlorinated esters and an ether of a low cost indigenous raw material, 3-pentadecenyl phenol, is described. These chlorinated products have been further evaluated in PVC compounds as secondary plasticizers.

INTRODUCTION

Chlorinated oil extracts, oil residues and fats' are considered as a most important group of plasticizer extenders, because of their low cost, low vapor pressure, flame resistance and excellent electrical properties. Due to the limited compatibility with vinyl resins, they are normally used in admixture with a primary plasticizer such as DOP. Apart from their important place in plastic industries, they are extensively used in cable, paint and metal lubricant industries.

Chlorinated products of phenol ethers' (Mollonc), hydrocarbon^,^ paraffin^,^ alkoxy benzene^,^ biphenyls,6 anthracene 3- pentadecenylphenyl acetate and 3-pentadecenylphenyl methyl ether,8 mineral oil9 etc. have been reported as plasticizer extenders

t NCL Communication No. 2962. $ Present Address: MIS. Ion Exchange (India) Ltd., M.I.D.C. Estate, Ambarnath,

Thana.

131

Dow

nloa

ded

by [

Uni

vers

ity o

f W

ater

loo]

at 0

6:51

10

Oct

ober

201

4

132 N. D. GHATGE, S . S. MAHAJAN AND S. V. VAIDYA

for PVC. In recent years, Cereclors (chlorinated paraffins) are widely used as plasticizer extenders in PVC.

In the present study the following compounds have been synthe- sized and evaluated as plasticizer extenders in PVC.

(1) Chlorinated 3-pentadecenylphenyl stearate. (2) Chlorinated 3-pentadecenylphenyl oleate. (3) Chlorinated 3-pentadecenylphenyl linoleate. (4) Chlorinated 3-pentadecenylphenyl phenyl ether.

EXPERIMENTAL

Preparation of esters and ether

The esters and ether were prepared from 3-pentadecenyl phenol as per the procedure described in our earlier communication. lo

General method for chlorination of esters and ether

Dry chlorine gas was passed through esters and ether at 0-5°C for a specified time (Table 11). Then the product was diluted with a suitable volume of carbon tetrachloride and dry nitrogen gas was passed through it at room temperature (to drive off excess of chlorine gas). Finally the solvent was distilled off to get the residual chlorinated product. The chlorination of unsaturated esters was carried out without any difficulties because fully chlorine saturated esters were pourable liquids at 0-5°C. In the case of 3- pentadecenylphenyl phenyl ether the aromatic nuclei were not fully saturated with chlorine at the end of the chlorination as at this stage the compound was very viscous.

The chlorination of these products was also carried out in solvent medium such as carbon tetrachloride but showed no advantage over direct chlorination without solvent. The elemental analysis of the respective chlorinated products is given in Table 11.

Compounding and testing

The compounding recipe used in the evaluation program of the chlorinated esters and ether of 3-pentadecenyl phenol, as extenders, is given in Table I.

Dow

nloa

ded

by [

Uni

vers

ity o

f W

ater

loo]

at 0

6:51

10

Oct

ober

201

4

EXTENDERS FOR POLYVINYL CHLORIDE 133

TABLE I Compounding recipe

No. Ingredients Parts

1 PVC resin" 100 2 Plasticizer DOP-extender (2/1) variable 3 White lead paste 8 4 Calcium stearate 1 5 Stearic acid 1

a A product of M/s. Sriram Vinyls, Kota, India having K value of 66.

Initially the extender was dissolved in a primary plasticizer (DOP) in the ratio of 1/2. Then the PVC resin was thoroughly mixed with plasticizer-extender mixture and other ingredients in a mixer.

The plasticizer-extender mixture was blended in the proportions of 40, 50, 60 and 70 parts with 100 parts of resin for evaluation. The compound was milled at 150°C for 6 minutes on a two roll mixing mill to give uniform sheet of thickness between 0.01 to 0.025 inch. The tensile strength, modulus, elongation and hardness were deter- mined at room temperature according to ASTM designations D-412- 68 and D-2240-68. The loss of plasticizer was determined according to ASTM designation D-1203 (61T) 1964. Volume resistivity was determined according to ASTM designation D-257-61 (1965).

DISCUSSION

Aliphatic monoesters and diesters have limited compatability with polyvinyl chloride. Chemical groups that enhance the solvency for PVC, i.e. 'Plasticizer-polymer interaction', are generally believed to increase the compatability while groups that interfere with solvency reduce the compatibility. The presence of polar and polarizable groups such as aromatic, halide, oxirane and ester in the plasticizer enhance the solvency for PVC. In our previous communication" we have reported esters and ether of 3-pentadecenyl phenol as plasticiz- er extenders in PVC. In the present study it was decided to incorporate polar groups in the esters and ether of 3-pentadecenyl phenol by chlorination and evaluate them as plasticizer extenders in PVC.

Dow

nloa

ded

by [

Uni

vers

ity o

f W

ater

loo]

at 0

6:51

10

Oct

ober

201

4

TA

BL

E I1

C

hlor

inat

ed e

ster

s an

d et

her

of 3

-pen

tade

ceny

l phe

nol

Tot

al p

erio

d re

quir

ed f

or

Cal

cula

ted

Foun

d ch

lori

natio

n N

atur

e of

C

H

CI

C

H

CI

N

o.

Com

poun

d (h

ours

) th

e pr

oduc

t (%

) (%

) (%

) (%

) (%

) (%

)

Ana

lysi

s

? P

I C

hlor

inat

ed 3

-pen

ta

dece

nylp

heny

l st

eara

te

I1

Chl

orin

ated

3-p

enta

de

ceny

lphe

nyl

olea

te

dece

nylp

heny

l 11

1 C

hlor

inat

ed 3

-pen

ta

4 Pa

le y

ello

w

55.3

1 7.

43

33.5

7 55

.29

7.29

33

.94

visc

ous

5 Pa

le y

ello

w

51.1

4 6.

55

38.9

0 51

.56

6.43

38

.29

visc

ous

8 Pa

le y

ello

w

47.5

5 5.

89

43.2

9 47

.49

5.76

43

.06

visc

ous

linol

eate

dece

nylp

heny

l phe

nyl

very

vis

cous

et

her

IV

Chl

orin

ated

3-p

enta

9

Pale

yel

low

-

-

-

46.5

5 4.

62

46.7

7

0

3:

Q 3 m F 3: > z e v, c

Dow

nloa

ded

by [

Uni

vers

ity o

f W

ater

loo]

at 0

6:51

10

Oct

ober

201

4

TA

BL

E 1

11

Phys

ical

pro

pert

ies

of t

he P

VC

com

poun

ds A

, B, C

, D, E

1.

2.

3.

4.

5.

6.

7.

8. H

ardn

ess

Ten

sile

str

engt

h (M

Pa)

100%

Mod

ulus

(MPa

) E

long

atio

n %

%

loss

in h

eatin

g w

ith

carb

on b

lack

at 7

0°C

fo

r 24

h

% lo

ss o

n ag

ing

in o

ven

at 1

00°C

for 2

4 h

% lo

ss in

1%

Soa

p So

lu-

tion

at 2

5°C

for

24

h V

olum

e re

sist

ance

at

25°C

(52

cm)

76

78

78

16.4

1 18

.27

17.0

3 12

.68

14.4

8 13

.03

210

150

220

1.22

5 -

1.27

2

8.06

2 -

7.56

3

0.12

63

-

0.12

47

9.00

5 x

10” -

9.74

7 x

10”

76

74

18.6

8 17

.86

15.0

3 13

.51

-

1.760

200

240

-

7.25

6

-

0.11

98

-

2.95

6 x

10’’

77

79

83

80

19.3

7 21

.18

22.2

0 17

.51

15.5

1 16

.75

18.0

0 13

.24

-

1.01

5 -

1.44

6 21

0 30

0 27

0 20

0

5.63

9 -

8.00

1 -

-

0.09

88

-

0.12

44

-

9.14

9 X

lo

’* -

6.37

2 x

10”

81

18.5

5 15

.72

190 -

-

-

-

A =

40

part

s of

mix

ture

of

DO

P: C

hlor

inat

ed 3

-pen

tade

ceny

lphe

nyl s

tear

ate.

B

= 4

0 pa

rts

of m

ixtu

re o

f D

OP:

Chl

orin

ated

3-p

enta

dece

nylp

heny

l ole

ate.

C

= 40

part

s of

mix

ture

of

DO

P: C

hlor

inat

ed 3

-pen

tade

ceny

lphe

nyl l

inol

eate

. D

= 4

0 pa

rts

of m

ixtu

re o

f D

OP:

Chl

orin

ated

3-p

enta

dece

nylp

heny

l phe

nyl e

ther

. E

= 4

0 pa

rts

of d

ioct

yl p

htha

late

. a

Bef

ore

agin

g.

Aft

er a

ging

at

100°

C fo

r 24

h.

Dow

nloa

ded

by [

Uni

vers

ity o

f W

ater

loo]

at 0

6:51

10

Oct

ober

201

4

TA

BL

E I

V

Phys

ical

pro

pert

ies

of t

he P

VC

com

poun

ds A

-I,

BI,

C-I

, D-I, a

nd E

-I

1. H

ardn

ess

74

76

73

74

70

72

75

78

76

79

2. T

ensi

le s

tren

gth

(MPa

) 15

.79

16.8

9 16

.13

17.6

5 16

.96

18.2

7 19

.51

20.4

1 16

.96

17.5

1 3.

100

% M

odul

us (

MPa

) 12

.34

13.7

2 11

.93

14.1

3 12

.89

14.9

6 16

.00

17.5

1 12

.62

14.4

8 4.

Elo

ngat

ion

%

230

210

250

230

260

240

350

290

260

230

5. %

loss

in h

eatin

g w

ith

1.68

7 -

1.77

3 -

1.66

3 -

1.28

5 -

1.87

7 -

6. 7

0 lo

ss o

n ag

ing

in o

ven

9.22

2 -

8.45

9 -

7.64

5 -

6.59

9 -

10.6

60

-

7. %

loss

in 1

% S

oap

0.17

00

-

0.16

99

-

0.15

66 -

0.12

72

-

0.21

01

-

carb

on b

lack

at

70°C

fo

r 24

h

at 1

00°C

for

24 h

Solu

tion

at 2

5°C

for

24 h

25°C

(Q

cm

)

A-I

= 5

0 pa

rts

of m

ixtu

re o

f D

OP:

Chl

orin

ated

3-p

enta

dece

nylp

heny

l ste

arat

e.

BI

= 5

0 pa

rts

of m

ixtu

re o

f D

OP:

Chl

orin

ated

3-p

enta

dece

nylp

heny

l ole

ate.

C

-I =

50

part

s of

mix

ture

of

DO

P: C

hlor

inat

ed 3

-pen

t~de

ceny

lphe

nyl li

nole

ate.

D-I

= 5

0 pa

rts

of m

ixtu

re o

f D

OP:

Chl

orin

ated

3-p

enta

dece

nylp

heny

l phe

nyl e

ther

. E

-I =

50

part

s of

dio

ctyl

pht

hala

te.

a B

efor

e ag

ing.

8. V

olum

e re

sist

ance

at

5.49

5 x

10” -

1.12

2 x

10” -

1.14

0 x

10l2

-

8.30

8 x

lo’*

-

4.80

0 x

10” -

Aft

er a

ging

at

100°

C fo

r 24

h.

Dow

nloa

ded

by [

Uni

vers

ity o

f W

ater

loo]

at 0

6:51

10

Oct

ober

201

4

TA

BL

E V

Ph

ysic

al p

rope

rtie

s of

the

PV

C c

ompo

unds

A-1

1, B-

11,

C-11

, D

-I1 a

nd E

-I1

A-I1

B

-I1

c-I1

D

-I1

E-I1

Ph

ysic

al p

rope

rtie

s (2

Ih

(1)”

(2

)”

(1)”

(2

P

(1)”

(a

b

(1)”

1. H

ardn

ess

69

70

70

72

68

70

68

71

65

68

2. T

ensi

le s

tren

gth

(MPa

) 14

.34

15.2

4 14

.48

15.7

9 15

.51

16.8

9 19

.17

20.1

3 14

.13

16.3

4 3.

100

% M

odul

us (

MPa

) 11

.10

12.0

0 11

.03

12.1

3 12

.13

13.1

0 15

.79

16.8

2 10

.13

11.2

4 4.

Elo

ngat

ion

%

260

230

260

250

280

250

380

310

270

240

5. %

loss

in h

eatin

g w

ith

2.09

6 -

1.94

6 -

1.74

2 -

1.33

2 -

2.17

8 -

6. %

loss

on

agin

g in

ove

n 11

.286

-

10.4

80

-

8.60

0 -

7.28

7 -

11.7

00

-

7. %

loss

in 1

% S

oap

0.20

93

-

0.19

64

-

0.19

56

-

0.13

75

-

0.27

37

-

carb

on b

lack

at 7

0°C

fo

r 24

h

at 1

00°C

for 2

4 h

Solu

tion

at 2

5°C

fo

r 24

h

25°C

(Q

cm

) 8.

Vol

ume

resi

stan

ce a

t 3.

677

X 10

” -

5.16

0 x

10” -

1.05

8 X

10

’’ -

6.96

6 X

10

” -

3.80

0 x

10” -

A-I1

=

60

part

s of

mix

ture

of

DO

P: C

hlor

inat

ed 3

-pen

tade

ceny

lphe

nyl s

tear

ate.

R

II =

60

part

s of

mix

ture

of

DO

P: C

hlor

inat

ed 3

-pen

tade

ceny

lphe

nyl o

leat

e.

C-I1

=

60

part

s of

mix

ture

of

DO

P: C

hlor

inat

ed 3

-pen

tade

ceny

lphe

nyl l

inol

eate

. D

-I1

= 6

0 pa

rts

of m

ixtu

re o

f D

OP:

Chl

orin

ated

3-p

enta

dece

nylp

heny

l phe

nyl e

ther

. E-

I1 =

60

part

s of

dio

ctyl

pht

hala

te.

a Se

fore

agi

ng.

Aft

er a

ging

at

100°

C fo

r 24

h.

Dow

nloa

ded

by [

Uni

vers

ity o

f W

ater

loo]

at 0

6:51

10

Oct

ober

201

4

TA

BL

E V

I Ph

ysic

al p

rope

rtie

s of

the

PV

C c

ompo

unds

A-I

II, B-111, C

-111

, D-

I11

and

E-I1

1

1.

2.

3.

4.

5.

6.

7.

8. H

ardn

ess

Ten

sile

str

engt

h

100%

Mod

ulus

(MPa

) E

long

atio

n %

%

loss

in h

eatin

g w

ith c

arbo

n bl

ack

at 7

0°C

for

24

h %

loss

on

agin

g in

ove

n at

100

°C

for 2

4 h

% lo

ss in

1%

soa

p solution a

t 25

°C

for

24 h

V

olum

e re

sist

ance

at

25°

C (Q

cm

)

(ma

)

68

68

66

69

62

65

65

69

61

63

13.3

7 14

.52

13.6

5 14

.96

14.8

2 16

.13

18.3

4 19

.65

12.0

6 14

.82

9.93

11

.24

9.65

11

.03

10.2

0 12

.20

14.4

8 15

.72

8.00

9.

93

2.45

0 -

2.24

1 30

0 27

0 32

0 30

0 36

0 31

0 42

0 34

0 30

0 27

0 -

2.09

2 -

1.72

2 -

2.48

0 -

12.0

40

-

11.7

63

-

10.0

53

-

8.03

4 -

11.5

40

-

0.27

32

-

0.22

26

-

0.20

03

-

0.15

00

-

0.30

21

-

2.58

0 X

10

" -

2.96

7 X

10

" -

9.89

1 x

10"

-

4.23

8 X

10

" -

2.58

3 X

10

" -

A-I

II =

70

part

s of

mix

ture

of

DO

P: c

hlor

inat

ed 3

-pen

tade

ceny

lphe

nyl s

tear

ate.

B-

111

= 7

0 pa

rts

of m

ixtu

re o

f D

OP:

chl

orin

ated

3-p

enta

dece

nylp

heny

l ole

ate.

C-

I11

= 7

0 pa

rts

of m

ixtu

re o

f D

OP:

chl

orin

ated

3-p

enta

dece

nylp

heny

l lin

olea

te.

D-11

1 =

70

part

s of

mix

ture

of

DO

P: c

hlor

inat

ed 3

-pen

tade

ceny

lphe

nyl p

heny

l eth

er.

E-I1

1 =

70

part

s of

dio

ctyl

pht

hala

te.

a B

efor

e ag

ing

Aft

er a

ging

at

100°

C fo

r 24

h.

Dow

nloa

ded

by [

Uni

vers

ity o

f W

ater

loo]

at 0

6:51

10

Oct

ober

201

4

EXTENDERS FOR POLYVINYL CHLORIDE 139

TABLE VII Percentage retention of the physical properties after aging of the PVC

compounds at 100°C for 24 h

Compound Tensile 100% No. Hardness strength Modulus Elongation

A B C D E A-I B-I c-I D-I E-I A-I1 B-I1 c-I1 D-I1 E-I1 A-I11 B-111 c-111 D-I11 E-111

102 102 104 105 101 102 101 102 104 104 101 102 102 104 104 104 104 104 106 103

111 109 108 105 105 107 109 107 104 103 106 109 108 105 115 109 109 108 107 122

114 115 114 107 118 110 118 113 109 114 103 110 108 106 110 113 114 119 108 124

71 90 87 90 95 91 92 92 82 86 88 96 89 81 88 90 93 88 80 90

The chlorinated esters and ether are pale yellow liquids of medium to high viscosity and have 33 to 46% chlorine content. When compounded with PVC for use as primary plasticizer, they were found to be less compatible than DOP. Therefore they were evaluated as secondary plasticizers in PVC.

The results in Tables I11 to VI indicate that all the chlorinated products of 3-pentadecenyl phenol in combination with DOP (prim- ary plasticizer) in the proportion of 112 show higher permanence than the PVC compounds where DOP alone is the plasticizer. This may be attributed to the polar nature of the compounds which possibly enhance their ability to tie up polar sites on the polymer chain. The higher strength and volume resistivity of the PVC compounds wherein chlorinated 3-pentadecenylphenyl phenyl ether has been used as secondary plasticizer may be due to its more polar nature (chlorine content 46%).

It would be seen from Table VII that the percentage retention of

Dow

nloa

ded

by [

Uni

vers

ity o

f W

ater

loo]

at 0

6:51

10

Oct

ober

201

4

140 N. D. GHATGE. S. S. MAHAJAN AND S. V. VAIDYA

the physical properties after aging of the PVC compounds (A to D) , (A-I to D-I), (A-I1 to D-II), (A-111 to D-111) wherein chlorinated esters and ether of 3-pentadecenyl phenol have been used are in good comparison with the PVC compounds (E, E-I, E-11, E-111) where DOP has been used as the only plasticizer.

CONCLUSION

The level of plasticizer required to produce a given hardness, flexibility or modulus is often used as a measure of efficiency. Thus the efficiency of the chlorinated products of 3-pentadecenyl phenol as plasticizer extender can be indicated as chlorinated 3- pentadecenyl phenyl oleate > chlorinated 3-pentadecenylphenyl stearate > chlorinated 3-pentadecenylphenyl linoleate > chlorinated 3-pentadecenylphenyl phenyl ether.

References

1 . A . W. Merkl, Ger. Offer. 2,008, 492 (Oct. 1970); C.A. 74, 4235f (1971). 2. 0. Pesta and F. Sinwel, Kunstsoffe 46, 155-57 (1956); C.A. 50, 11053c (1956). 3. A . Gislon and J . Quiquerez U.S. 2,588, 177 (June 26 1951); C.A. 45, 8807h

4. D. G. Boller, Oflic. Activ. Plast. Caout. 14 (5), 449-62 (1967) (Fr.); C.A. 67,

5. G. K. Storin, F. E. Lawlor and F. Casciani. U.S . 2,814, 602 (Nov. 26 1957);

6. M. Fournier and X. Thiesse. In&. Plastiques 4, 176-82 (1948); C.A. 43, 436b

7. M. Ya. Feldman and A. I. Krymova, USSR 65, 704 (Jan. 31, 1946); C.A. 41,

8. N. D. Ghatge and S. P. Vernekar, Eur. Polym. J . 6 , 1547-52 (1970). 9. S. A. Qureshi, A . H. Z. Yousufzai and Shabih-ul-Hassan, Pak. J . Sci. Ind. Res.

10. N. D . Ghatge and S. V. Vaidya, Die Angewandte Makromolekulare Chemie. 43,

(1951).

44359111 (1967).

C.A. 52, 5040h (1958).

(1949).

1879f (1947).

l3 (4), 461-2 (1970) (Eng.).

1-10 (1975). Dow

nloa

ded

by [

Uni

vers

ity o

f W

ater

loo]

at 0

6:51

10

Oct

ober

201

4