5 Random Copolycarbonates: Characterization and Downloaded by UNIV OF CALIFORNIA SANTA BARBARA on May 26, 2018 | https://pubs.acs.org Publication Date: June 1, 1974 | doi: 10.1021/bk-1974-0004.ch005
Comparative Properties of Polymers Containing Tetrachlorinated Bisphenols E U G E N E C . G I L B E R T and G O R D O N D . B R I N D E L L John Stuart Research Laboratories, The Quaker Oats Co., Barrington, Ill. 60010
Abstract Several 2,2',6,6'-tetrachloro-4,4'-dihydroxy bisphenols were subjected to random copolymerization with bisphenol A at two levels of incorporation. Copolymerization of TCBF with isomeric chlorinated bisphenols was a l s o carried out. Original, as well as aged physicals, were o b t a i n e d for all of t h e copolycarbonates e x c e p t TCBF. T h e most interesting properties were obtained from copolymers o f TCBF u n d e r t h e conditions studied. Copolymers containing TCBF possessed properties t h a t in general were e q u a l t o or better t h a n either bisphenol A or tetrachlorobisphenol A homopolycarbonates, e . g . , t h e bisphenol A copolymer containing 7 0 % TCBF was f o u n d t o h a v e a T g of 1 9 0 ° C . This latter copolycarbonate, as well as that p r e p a r e d f r o m TCBF a n d a mixture o f chlorinated isomers had significantly better stress cracking resistance to perchlorinated hydrocarbon solvents than either bisphenol A or tetrachlorobisphenol A homopolymers. The r e c e n t d i s c o v e r y (1) o f an improved s y n t h e s i s o f i s o m e r i c a l l y p u r e 2 , 6 - d i c h l o r o p h e n o l (2,6-DCP) i n h i g h yield f r o m pyrolysis of 2,2,6,6-tetrachlorocyclohexanone inevitably l e d t o t h e subsequent p r e p a r a t i o n o f v a r i o u s monomers f o r u s e a s building blocks i n polymer s y n t h e s i s ; a r e p r e s e n t a t i o n o f t h e type o f i n t e r m e d i a t e s p o s s i b l e i s p r e s e n t e d i n Scheme I . S e v e r a l t y p e s o f p o l y m e r s b a s e d on 2,6-DCP and its d e r i v a t i v e s have been p r e v i o u s l y p r e p a r e d . These i n c l u d e p o l y p h e n y l e n e o x i d e s (2) f r o m r e a c t i o n o f 2,6d i c h l o r o - 4 - b r o m o p h e n o l , p o l y s u l f o n a t e s (3) based on 2 , 6 - d i c h l o r o - 4 - b e n z e n e s u l f o n y l c h l o r i d e , and p o l y e s t e r s (4) formed v i a c o n d e n s a t i o n o f 3 , 5 - d i c h l o r o - 4 49
Deanin; New Industrial Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1974.
Deanin; New Industrial Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1974.
THoOH
2
b
LOJ
OH C L l ^ l
^3H^>
Intermediates based on 2,6-DCP*
2
2
2
2
2
3
l
CI
b
2
?
CH -( HOH((70)
2
\
b
b
R = H (80) GH CH OH ( 7 5 )
CI
R = H (90) = CH CH OH (75)*> = CH2-CH-OH ( 7 0 ) R = H (90) J COOH R - alkyl = CH CH OH (70) CH a) Numbers i n p a r e n t h e s e s a r e minimum y i e l d s (%) a t t a i n a b l e (not o p t i m i z e d ) b) Y i e l d s based on s t a r t i n g m a t e r i a l where R = H.
Scheme I.
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5.
GILBERT
AND
BBiNDELL
Random
Copolycarbonates
51
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hydroxybenzoic a c i d . More r e c e n t l y , p o l y ( 3 , 5 - d i c h l o r o 4-methylenephenylene e t h e r ) , a h i g h temperature polymer based on 3 , 5 - d i c h l o r o - 4 - h y d r o x y b e n z y l c h l o r i d e , has a l s o been s y n t h e s i z e d and s t u d i e d ( 5 ) . Foremost among t h e monomers p r e p a r e d from 2,6-DCP, however, a r e t h e b i s p h e n o l i c i n t e r m e d i a t e s . S e v e r a l o f these, along w i t h t h e i r a p p r o p r i a t e chemical abbrev i a t i o n s , a r e i l l u s t r a t e d below: X = CH X = S0 X = CH OCH
TCBF TCBS TCBF-0
2
2
2
2
Y
Z
•e X = CH -N~CH I OH-* 2
where
2
9
TCBF-MA salts
Y = H, Z = CI Y = CH , Z = C H S 0 3
3
4
TCBF (6), TCBS (7) and TCBF-0 (£) have been p r e v i o u s l y d e s c r i b e d ; TCBF-MA and i t s s a l t s , however, a r e new c o m p o s i t i o n s . A comparison o f m e l t i n g p o i n t s o f t h e above b i s p h e n o l s t o some which a r e more w e l l known i n t h e l i t e r a t u r e i s p r e s e n t e d i n T a b l e 1. A l t h o u g h m e l t i n g p o i n t s o f monomers need bear no d i r e c t r e l a t i o n s h i p t o polymer morphology, t h e y may w i t h a knowledge o f monomer s t r u c t u r e , p r o v i d e some i n s i g h t c o n c e r n i n g what may be e x p e c t e d i n polymer systems i n g e n e r a l . T h i s i s based on t h e thermodynamic e q u a t i o n , A G = AH - T A S , which a t t h e m e l t i n g p o i n t l e a v e s A = 0, s i n c e we have an e q u i l i b r i u m s i t u a t i o n . T then i s e q u a l t o A H / A S . I f one assumes A H t o be c o n s t a n t f o r t h i s s e r i e s o f compounds, t h e m e l t i n g p o i n t w i l l be a s i m p l e f u n c t i o n o f e n t r o p y change as t h e monomer p r o c e e d s from t h e s o l i d t o t h e l i q u i d s t a t e (and v i c e - v e r s a ) . S m a l l e n t r o p y changes due t o i n c r e a s e d symmetry w i l l r e s u l t i n h i g h e r T . One may then r e l a t e t h i s t o t h e a b i l i t y o f t h e m o l e c u l e s t o pack t o g e t h e r once i n c o r p o r a t e d i n polymer c h a i n s and hence, make a p r i o r i p r e d i c t i o n s as t o what t o e x p e c t i n such systems. While n o t f o o l p r o o f , i t i s , n e v e r t h e l e s s , a u s e f u l technique. From t h e m e l t i n g p o i n t comp a r i s o n , one may t h e n p r e d i c t t h a t s e v e r a l o f t h e new b i s p h e n o l i c types w i l l , i f s u c c e s s f u l l y i n c o r p o r a t e d , m
r o
m
m
m
m
m
m
Deanin; New Industrial Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1974.
52
NEW
INDUSTRIAL
POLYMERS
i m p a r t s i g n i f i c a n t c r y s t a l l i n e c h a r a c t e r t o b o t h homopolymers and copolymers. T h i s argument i s f u r t h e r r e i n f o r c e d by s t e r i c ( c h l o r i n e v e r s u s hydrogen) and p o l a r i t y c o n s i d e r a t i o n s which s h o u l d t e n d t o r e s t r i c t r o t a t i o n o f the polymer c h a i n and a l s o , t h e r e b y , p r o v i d e f o r h i g h e r Tg's.
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TABLE I Comparison o f M e l t i n g P o i n t s f o r V a r i o u s p h e n o l s and S e l e c t e d D e r i v a t i v e s Bisphenol
M.P.,
a
TCBA TCBF-0 BA TBBA TCBF-MA TCBF TCBF-MA (DMS BS
