Acrylic Modification of Plasticized Poly(vinyl chloride) - Advances in

7 Acrylic Modification of Plasticized

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Poly(vinyl chloride) JOHN

T. LUTZ, JR.

R o h m and Haas C o . , Research Laboratories, P . O . Box 219, Bristol, P a . 19007

Acrylic, methacrylate butadiene styrene (MBS), and acrylo nitrile butadiene styrene (ABS) modifiers are commonly used in rigid PVC to improve processing and physical prop erties. Although plasticized PVC is generally easy to process and properties are readily adjusted through plasticizer type and concentration, the modifiers are useful for imparting unusual combinations of properties. The acrylic and MBS impact modifiers are the more effective for improving the low temperature flexibility of semi-rigid and polymeric plas ticized systems, thereby permitting the use of more perma nent plasticizers and the attainment of low temperature properties normally associated with the use of the non permanent monomeric plasticizers. By using the proper acrylic or MBS modifier, abnormally highfillercontents can be used in plasticized PVC compounds without excessive loss of physical properties. " p o l y ( v i n y l chloride)

( P V C ) is a v e r s a t i l e p o l y m e r p r i m a r i l y because

it c a n b e m o d i f i e d to p r o d u c e c o m p o u n d s n u m b e r of diverse properties.

h a v i n g a n almost infinite

R i g i d ( unplasticized ) P V C products are

the most difficult to p r o d u c e because of t h e p o o r cohesion of h o t P V C u n d e r shear. Since 1955, a g r o w i n g f a m i l y o f a c r y l i c modifiers has m a d e p r o c e s s i n g of r i g i d P V C m u c h easier a n d m o r e e c o n o m i c a l ( b y i m p r o v i n g h o m o g e n e i t y , h o t strength, a n d e l o n g a t i o n )

a n d has m a d e i t possible to

p r o d u c e r i g i d p r o d u c t s w i t h v e r y h i g h i m p a c t strength. A l t h o u g h t h e use of t h e a c r y l i c modifiers i n r i g i d P V C is n o w c o m m o n p l a c e , t h e i r c o n t r i b u t i o n s to q u a l i t y a n d p e r f o r m a n c e i n p l a s t i c i z e d P V C are still not fully utilized.

Since e x p o s i t i o n of e a c h of t h e several

types o f a c r y l i c modifiers w o u l d m e r i t a p a p e r of its o w n , w e w i l l o n l y o u t l i n e t h e u t i l i t y of e a c h a n d d e v o t e the r e m a i n d e r of this p a p e r t o t h e uses o f i m p a c t modifiers i n p l a s t i c i z e d P V C . 61 In Fillers and Reinforcements for Plastics; Deanin, R., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1974.

62

FILLERS A N D R E I N F O R C E M E N T S FOR PLASTICS

Table I.

Effects of Modifier on Low

Shore A Hardness

Modifier

Material Di(2-ethylhexyl) adipate , δ = 8.48" 1 0 % Modifier

Temperature

Flexibility T , °C f

Impact T ,°C B


8

77-76 79-76 75-73 75-73

-51 -55 -53 -53

-58 -61 -57 -57

ACR MBS-11 ABS-2

82-80 76-76 76-76

-64 -55 -55

-62 -67 -57

ACR MBS-11 ABS-2

83-80 85-82 85-81 84-81

-19 -25 -25 -25

-30 -34 -33 -33

ACR MBS-11 ABS-2

87-79 79-76 79-77

-29 -27 -27

-43 -43 -43

ACR MBS-11 ABS-2

90-88 80-87 87-85 88-86

-

4 5 7 7

-11 -18 -22 -20

ACR MBS-11 ABS-2

88-85 86-83 86-84

-12 -12 -11

-22 -31 -18

ACR MBS-11 ABS-2 1

1 4

2 0 % Modifier

Di(2-ethylhexyl) phthalate, δ = 8.9 1 0 % Modifier

2 0 % Modifier

P o l y e s t e r , δ = 9.2 10% Modifier

2

5

2 0 % Modifier

° Seven days/60°C, 0.5 psi, natural foam latex rubber. Solubility parameter, after the method of Burrell and Small (4).

6

Processing A i d s : Faster fusion, especially w i t h polymeric plasticizers G r e a t e r hot strength a n d r o o m t e m p e r a t u r e toughness I m p r o v e d c a l e n d e r t r a c k i n g a n d sheet q u a l i t y R e d u c t i o n or e l i m i n a t i o n of p l a t e - o u t S t a b i l i z a t i o n of c e l l s t r u c t u r e i n foams Impact Modifiers: I m p r o v e m e n t i n l o w t e m p e r a t u r e toughness w i t h o u t sacrificing m o d u l u s or p e r m a n e n c e I m p r o v e m e n t of flex f a t i g u e resistance a n d r e t e n t i o n of tensile p r o p erties even at h i g h filler levels I m p r o v e d d r a p e a n d d r i e r f e e l of h i g h l y p l a s t i c i z e d P V C Lubricant-Processing Aids : G o o d release f r o m h o t m e t a l , b u t essentially n o n - m i g r a t o r y at r o o m temperature

In Fillers and Reinforcements for Plastics; Deanin, R., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1974.

7.

L U T Z , JR.

PVC

1 0 ,

Acrylic

Ultimate Elongation, %

63

of PVC

Containing 50 phr Plasticizer

Tensile Strength, psi


Modification

0

100%

Modulus, ρή

Migration into Foam Rubber, %"

2500 2300 2300 2100

405 375 380 310

1100 1000 1000 1100

2200 2200 2100

330 350 320

900 900 1000

2600 2600 2700 2500

400 460 470 400

1700 1400 1400 1500

13.0 13.1 13.2 14.3

2500 2600 2400

440 510 470

1300 1200 1400

13.5 13.7 15.6

3100 3100 3100 2700

400 420 435 350

2400 2000 2000 2000

0.4 0.5 0.5 0.7

2900 2900 2700

430 460 360

1700 1600 1700

0.5 0.6 0.7

' F o r reference: S P V C = 9.7; G R S = 8.1; M M A = 9.5. * Superscript numbers refer to compounds listed in text.

Flatting Agents: G o o d d u l l i n g of surfaces w i t h o u t sacrifices i n p h y s i c a l p r o p e r t i e s o r s o i l resistance Reactive Monomers: I m p a r t l o w v i s c o s i t y to P V C / p l a s t i c i z e r dispersions a n d y i e l d h a r d , t o u g h , heat-resistant p r o d u c t s D e t a i l e d p e r f o r m a n c e s of the p r o c e s s i n g a i d s a n d r e a c t i v e m o n o m e r s i n plasticized P V C are presented elsewhere Types of Impact

(1,2,3).

Modifiers

T h r e e types of i m p a c t modifiers are a v a i l a b l e : A . A l l acrylic ( A C R ) B . M e t h a c r y l a t e b u t a d i e n e styrene ( M B S ) C . A c r y l o n i t r i l e b u t a d i e n e styrene ( A B S )


64

FILLERS

AND REINFORCEMENTS

FOR

PLASTICS

W i t h i n each group, the composition a n d quantity of the rubbery a n d h a r d phases c a n b e v a r i e d to r e g u l a t e p e r f o r m a n c e , r e f r a c t i v e i n d e x , etc.

M o s t of t h e c o m p o s i t i o n a l i n f o r m a t i o n has n o t b e e n d i s c l o s e d , a n d

since t h e c o m p l e x i t y of the p o l y m e r s p r e c l u d e s m e a n i n g f u l c a l c u l a t i o n of s o l u b i l i t y parameters o r other expressions that w o u l d c l e a r l y define t h e m o d e o f o p e r a t i o n o f the modifiers, this presentation w i l l b e a p r a g m a t i c


one. Interaction of Plasticizer

Type and Modifier

Type and

Concentration

T h e d a t a i n T a b l e I i l l u s t r a t e t h e effects of m o d i f i e r t y p e a n d c o n centration o n the physical properties

of P V C compounds

plasticized

w i t h 50 p h r (parts p e r h u n d r e d o f resin—i.e., P V C - f m o d i f i e r ) o f three plasticizers o f v a r y i n g s o l u b i l i t y parameters ( δ ). T h e effect of p l a s t i c i z e r t y p e is m u c h m o r e d r a m a t i c o n t h e properties of t h e u n m o d i f i e d P V C t h a n is t h e t y p e o f modifier. compatible

Modified compounds

c o n t a i n i n g t h e least

( w i t h P V C ) plasticizer, di(2-ethylhexyl)

adipate

(DOA),

s h o w t h e least i m p r o v e m e n t i n l o w t e m p e r a t u r e p r o p e r t i e s a n d t h e most •c + 25 ρ

Ο

+ 20

KEY Οχ UNMODIFIED 5* 5 % MODIFIER 10* 1 0 % 20» 2 0 %

+ 15

+ 10

MBS-II

+5 0 -5 -10

-15 -20-25 -30 -35 -40 25 PHR

POLYESTER

Figure 1.

50

75

PLASTICIZER

Brittle point



7.

L U T Z , JR.

Acrylic

Modification

impairment i n physical properties.

of

65

PVC

G e n e r a l l y , b o t h the A C R a n d M B S

modifiers are s i g n i f i c a n t l y better t h a n the A B S modifiers for o v e r a l l performance. W i t h the m o r e c o m p a t i b l e p l a s t i c i z e r s , D O P a n d the

polyesters,

a d d i t i o n of the A C R a n d M B S modifiers results i n greater i m p r o v e m e n t s i n l o w t e m p e r a t u r e properties

( e s p e c i a l l y i m p a c t resistance)

impairment i n physical properties.

without

T h e a d d i t i o n of the A B S m o d i f i e r ,

h o w e v e r , consistently results i n i m p a i r e d tensile strength a n d g e n e r a l l y i m p a i r e d elongation along w i t h the general improvement i n l o w temperature properties. T h e greatest i m p r o v e m e n t i n l o w t e m p e r a t u r e properties is a c h i e v e d b y a d d i n g M B S modifiers to P V C p l a s t i c i z e d w i t h polyester p l a s t i c i z e r s . E x t r a c t i o n a n d m i g r a t i o n resistance of the c o m p o u n d are not s i g n i f i c a n t l y impaired. T h u s , two antagonistic properties—permanence and l o w temperature

flexibility—can

b e i m p a r t e d to a flexible c o m p o u n d t h r o u g h the

use of a polyester p l a s t i c i z e r a n d a n a c r y l i c i m p a c t m o d i f i e r — e s p e c i a l l y of the M B S t y p e .


66

F I L L E R S A N D R E I N F O R C E M E N T S F O R PLASTICS

Interaction

of Plasticizer

Concentration

and Modifier

Level

P V C ' s c o n t a i n i n g 2 5 , 50, a n d 75 p h r polyester p l a s t i c i z e r a n d t h e M B S m o d i f i e r at levels of 0, 5, 10, a n d 2 5 % h a v e b e e n chosen as t h e model

system.

Improvement

i n l o w temperature

impact

resistance


( b r i t t l e p o i n t , F i g u r e 1 ) is n o t l i n e a r w i t h i n c r e a s i n g m o d i f i e r content. The

greatest

fier,

and

percentage

t h e greatest

improvement

is a c h i e v e d

numerical improvement

with

1 0 % modi-

is a c h i e v e d

at 2 0 %

m o d i f i e r ( w i t h i n t h e l i m i t s o f this s t u d y ) . T h e greatest c o n t r i b u t i o n s of t h e m o d i f i e r a r e o b t a i n e d at t h e lowest p l a s t i c i z e r c o n c e n t r a t i o n — o r , w h e r e i t is n e e d e d most. psi KEY 0 « UNMODIFIED 5» 5% MODIFIER 10 «10% 20 «20%

7000 0 1 \

500 6000

-

500

4

5000

\\

500 4000 500 3000

\\ \\

-

\\

\\

500

X

^J^5,I0 20

2000 25

50

75

PHR POLYESTER PLASTICIZER

Figure 3.

Tensile

strength

M o d u l u s ( F i g u r e 2 ) a n d tensile s t r e n g t h ( F i g u r e 3 ) s h o w t h e most significant r e d u c t i o n s at t h e l o w e s t p l a s t i c i z e r c o n c e n t r a t i o n . E l o n g a t i o n ( F i g u r e 4 ) , h o w e v e r , has a s o m e w h a t different response.

Incorporation

of 2 0 % m o d i f i e r i n t h e 2 5 p h r p l a s t i c i z e r c o m p o u n d results i n d r a m a t i c i m p r o v e m e n t i n e l o n g a t i o n . A t 50 p h r p l a s t i c i z e r , t h e effects of m o d i f i e r e v e n at 2 0 % are q u i t e s m a l l .

Significant improvements i n elongation

t h r o u g h i n c r e a s e d m o d i f i e r content a r e a g a i n o b t a i n e d w i t h 7 5 p h r p l a s t i cizer. A

T h e a d d i t i o n of m o d i f i e r results i n s l i g h t l y softer stocks

hardness, F i g u r e 5 ) , w i t h t h e differences

(Shore

b e i n g m i n i m i z e d as t h e

p l a s t i c i z e r c o n c e n t r a t i o n is i n c r e a s e d .


7.

L U T Z , JR.

Acrylic

Modification

67

of PVC

600 50 500


50 400 50 300 50 200 50 100 50 25 PHR

Figure 4. Potential Applications

50

75

POLYESTER PLASTICIZER

Utilizing

Ultimate

elongation

Modifiers

V a r i o u s types o f pressure-sensitive tapes a n d foils r e q u i r e t h e use of m e d i u m - t o - h i g h m o l e c u l a r w e i g h t polyester p l a s t i c i z e r s t o p r e v e n t m i g r a t i o n f r o m t h e P V C film into t h e adhesive mass. F r e q u e n t l y a c c o m p a n y i n g this r e q u i r e m e n t is t h e n e e d f o r g o o d l o w t e m p e r a t u r e i m p a c t resistance. A specific e x a m p l e of a p r o d u c t t h a t w o u l d benefit f r o m t h e use o f t h e i m p a c t modifiers is e l e c t r i c a l tapes

(Table I I ) . Improvements

in low

t e m p e r a t u r e properties w e r e p r e v i o u s l y o b t a i n e d i n this t y p e of f o r m u l a t i o n b y r e p l a c i n g p a r t of t h e p o l y m e r i c p l a s t i c i z e r w i t h a m o n o m e r i c l o w t e m p e r a t u r e p l a s t i c i z e r s u c h as d i i s o d e c y l a d i p a t e .

T h e use of t h e

a c r y l i c i m p a c t modifiers c a n result i n e q u a l o r greater i m p r o v e m e n t i n l o w t e m p e r a t u r e properties w i t h o u t i n t r o d u c i n g m i g r a t o r y

monomeric

pasticizers that destroy a d h e s i o n . S e m i - r i g i d P V C sheet is b e i n g u s e d i n m a n y a p p l i c a t i o n s r e q u i r i n g a h i g h d e g r e e of toughness.

B o o k covers, f o r e x a m p l e , m u s t h a v e g o o d

resistance to flex fatigue a n d b e l o w i n cost.

T h e a d d i t i o n of a c r y l i c

modifiers to P V C c o m p o u n d s c o n t a i n i n g 2 0 p h r D O P a n d 18 p h r C a C 0 filler MBS

3

gives s u b s t a n t i a l i m p r o v e m e n t s i n flex l i f e ( F i g u r e 6 ). I n this area, modifiers

appear

to b e m o r e

effective

than all-acrylic ( A C R )

modifiers, b u t b o t h are s u b s t a n t i a l l y m o r e effective t h a n A B S .


68

FILLERS A N D REINFORCEMENTS

F O R PLASTICS

HARDNESS

100 ρ 8 6 4

-

2 90 8 -


6 4 -

2 80 8 6 4

-

2 70 8 6 4 -

2 60 L

PHR

Figure 5.

Table II.

POLYESTER

PLASTICIZER

Shore A hardness, 10 sec

Effects of Modifiers in Electrical Tapes Modifier MBS11, io%

ACR, 20%

MBS11, 20%

Property

0%

ACR, 10%

Shore A hardness Tensile strength, p s i U l t i m a t e elongation, % 5 0 % Modulus, psi 100% Modulus, psi Tf, ° C T , °C Masland impact, ° C D i e l e c t r i c s t r e n g t h " , ν/mil; 0.2 i n . electrodes i n a i r : A t 23 ° C % R e t e n t i o n after 24 h r in distilled water at 23°C

87-83 2800 350 1100 1700 -10 -17 - 8

86-82 2800 350 1100 1500 -10 -23 -10

84-80 2800 375 1000 1400 -10 -23 -12

83-79 2500 320 900 1300 -16 -26 -15

83-79 2400 370 800 1100 -15 -26 -21

1930

1770

1790

1840

1710

86

78

74

67

65

B

e

Determined on 7- mil film; other tests run on 75-mil panels. Formulation: 100-X P V C X Modifier 55 Polyester plasticizer 4 Lectro 60 ( N / L Industries) 0.6 Polyethylene, AC-629 1.0 Micronex Black (ground in Paraplex G-59) Superscript numbers refer to compounds listed in text. α

1 2 6

6

6


7.

L U T Z , JR.

Acrylic

Modification

of

69

PVC

I n a d d i t i o n to i m p r o v e m e n t s i n flex l i f e , the use of the M B S modifiers provides

a means

of

adjusting physical properties without changing

p l a s t i c i z e r levels ( T a b l e I I I ) . T h e use of h i g h levels of filler is f r e q u e n t l y d e s i r e d to l o w e r cost a n d to i m p a r t c e r t a i n other properties s u c h as flame r e t a r d a n c e .

The

2600


FORMULATION 100-X PVC X MODIFIER 20 OOP 18 ATOMITE Modifier, Plasticizer 60 , Filler , phr lz

a

a

6

1


b

Property

0

50

75

0

50

Shore A hardness Tensile strength, psi U l t i m a t e elongation, %

73 1700 375

76 1600 370

76 1500 355

76 1500 280

77 1100 230

a 6

c

Monoplex S-75 (high molecular weight epoxidized e s t e r ) / T O T M = Formulation: P V C modifier/plasticizer/Ti0 /stabilizer/Atomite indicated/5/2/as indicated. Superscript numbers refer to compounds listed in text. 1 1

2

1/1. = 70/30/as

a c r y l i c resins h a v e the a b i l i t y to '*bind i n " fillers a n d p i g m e n t s as e v i d e n c e d b y t h e i r d r a m a t i c effects o n e H m i n a t i n g plate-out.

T h i s effect

also p e r m i t s one to i n c o r p o r a t e v e r y h i g h levels of filler into p l a s t i c i z e d P V C w i t h o u t seriously i m p a i r i n g tensile p r o p e r t i e s .

I n the c o m p a r i s o n s

i n T a b l e I V , the c o m p o u n d c o n t a i n i n g 3 0 % M B S a n d 75 p h r C a C 0

has

3

greater e l o n g a t i o n a n d e q u i v a l e n t tensile strength a n d hardness w h e n c o m p a r e d w i t h the c o m p o u n d c o n t a i n i n g 3 0 % A B S a n d no

filler.

The

cost savings t h r o u g h the use of M B S over A B S b e c o m e i m m e d i a t e l y obvious. Finally, compounds and

recent

developments

i n automotive

that h a v e g o o d d i m e n s i o n a l s t a b i l i t y a n d l o w t e m p e r a t u r e i m p a c t

resistance.

B u m p e r filler strips or sight-shields, f e n d e r extensions, etc. Table V .

Sag Resistant-Low Temperature Impact Resistant Compounds Compound

Compound PVC '" M B S modifier DOP DOA DDA Paraplex G - 6 2 Stabilizer A l u m i n u m pigment Shore D hardness 1 0

2

T , °c B

Sag index ( X a b

applications require

t h a t are i n e x p e n s i v e (as r a w m a t e r i a l s a n d i n f a b r i c a t i o n )

10-")

6

450

451

100 0 38.7 0 0 4.3 2.3 2.0 52-45 -14 16

100 0 0 30.6 0 4.3 2.3 2.0 54-48 -24 10

452

No. 453

80 90 20 10 0 0 22.5 22i5 0 0 2.5 2.5 2.3 2.3 2.0 2.0 62-55 64-58 -24 -47 8 6.3

Superscript numbers refer to compounds listed in text. Sag index = inches of sag/°C/seconds to sag 3 inches.


455 80 20 0 0 22.5 2.5 2.3 2.0 64-58 -50 5

7.

L U T Z , JR.

Acrylic

Modification

of

71

PVC

m u s t resist d e f o r m a t i o n at e l e v a t e d temperatures i n service a n d m u s t s u r v i v e i m p a c t over a range of temperatures. O b v i o u s advantages for P V C c o m p o u n d s are cost a n d the ease of i n j e c t i o n m o l d i n g or e x t r u d i n g parts t h a t c a n be i n t e g r a l l y c o l o r e d finished

w i t h o u t pretreatment.

be stiff e n o u g h to resist s a g g i n g a n d s t i l l h a v e g o o d l o w

temperature

p r o p e r t i e s c a n o n l y b e a c c o m p l i s h e d , w e b e l i e v e , t h r o u g h the Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on November 24, 2015 | http://pubs.acs.org Publication Date: June 1, 1974 | doi: 10.1021/ba-1974-0134.ch007

or

D e v e l o p i n g P V C c o m p o u n d s that w i l l proper

selection of p l a s t i c i z e r a n d a c r y l i c i m p a c t modifier. T h e d a t a i n T a b l e V i l l u s t r a t e the possibilities of d e v e l o p i n g

com-

p o u n d s t h a t w i l l h a v e a b r i t t l e t e m p e r a t u r e of — 5 0 ° C ( — 5 8 ° F ) w h i l e b e i n g stiff e n o u g h to resist s a g g i n g i n a c a n t i l e v e r test at temperatures u p to a b o u t 4 0 ° - 5 0 ° C ( 1 0 4 ° - 1 2 2 ° F ) i n a 7 0 - m i l t h i c k flat section.

Con-

ventionally plasticized and unmodified compounds having brittle temperatures of o n l y — 2 4 ° C ( — 1 2 ° F ) l i t e r a l l y c o l l a p s e at temperatures of 32°-37°C (90°-98°F). Conclusions A f a m i l y of a c r y l i c modifiers for p l a s t i c i z e d P V C is a v a i l a b l e t o : ( 1 ) M a k e processing easier a n d m o r e e c o n o m i c a l . ( 2 ) I m p a r t s p e c i a l effects s u c h as l o w gloss w i t h o u t sacrificing s o i l resistance a n d p h y s i c a l properties. ( 3 ) A l l o w c o m p o u n d e r s to d e v e l o p c o m p o u n d s h a v i n g antagonistic properties s u c h as: ( a ) g o o d p e r m a n e n c e a n d g o o d l o w t e m p e r a t u r e flexibility; ( b ) sag resistance a n d stiffness p l u s excellent l o w t e m p e r a t u r e i m p a c t resistance; ( c ) stiffness a n d g o o d flex fatigue resistance; ( d ) l o w cost t h r o u g h h i g h filler loadings w i t h o u t major sacrifices i n tensile properties. W e feel that w e h a v e o n l y u n c o v e r e d the t i p of the i c e b e r g w h e n i t comes to the advantages of u s i n g the a c r y l i c modifiers.

W e hope that

c o m p o u n d e r s w i l l h e l p u n c o v e r the rest t h r o u g h i m a g i n a t i v e use i n t h e i r work. Materials ( 1) (2) (3) (4) (5) (6) (7) (8) (9) (10) ( 11 )

Used

A c r y l o i d K M - 3 2 3 — a l l acrylic modifier A c r y l o i d K M - 6 1 1 — M B S modifier A c r y l o i d K M - 2 2 9 — M B S modifier E x p e r i m e n t a l modifier 6 8 1 9 - X P — M B S modifier ParaplexG-54—polyester ParaplexG-59—polyester Paraplex G - 6 2 — e p o x i d i z e d soybean o i l D O A — d i ( 2-ethylhexyl ) adipate D D A — D i i s o d e c y l adipate Polyvinyl c h l o r i d e ) , A S T M D-1755-66, T y p e G P - 6 0 5 0 0 0 P o l y ( v i n y l c h l o r i d e ) A S T M D-1755-66, T y p e G P - 4 0 5 0 0 0


72 (12) (13) (14)

FILLERS A N D REINFORCEMENTS FOR PLASTICS

P o l y ( v i n y l c h l o r i d e / v i n y l acetate), A S T M D-2747-66T, T y p e C118360 A B S - 1 , A S T M D-1778-68, T y p e 543 A B S - 2 , A S T M D-1788-68, T y p e 611


Literature Cited 1. Lutz, J. T., Jr., Society of Plastics Engineers, Annual Technical Conference (May 1970). 2. Lutz, J. T., Jr., Mod. Plastics (1971) 48(5), 78-80. 3. Lutz, J. T., Jr., Plastics Design Proc. (Sept. 1971) 30-33. 4. Burrell, H., Small, Interchem. Rev. (Spring 1955) 3-46. RECEIVED October 11, 1973.


Acrylic Modification of Plasticized Poly(vinyl chloride) - Advances in

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