Polymer Bulletin 7, 1 2 3 - 1 2 8 (1982) P o l y m e r B u l l e t i n

9 Springer-Verlag 1982
Net wor k For mat i on I nvol vi ng Epoxi de and
Carboxyl Gr oups
Course of the Model Reaction Monoepoxide-Monocarbonic Acid
Libor Mat6jka, Svatopluk Pokom9 and Karel Du!iek
Institute of Macromolecular Chemistry, Czechoslovak Academy of Sciences,
CS-162 06 Prague 6, Czechoslovakia
Sr munar y
The ba s e c a t a l yz e d r e a c t i on be t we e n e poxi de a nd
c a r boxyl gr oups wa s s t udi e d us i ng a s i mpl e mode l s ys t e m
phe nyl gl yc i dyl e t he r - c a pr oi c a c i d i n t he pr e s e nc e of
t r i e t hyl a mi ne . The r e a c t i on wa s i nve s t i ga t e d by ma s s
s pe c t r ome t r y a nd GPC whi c h pr ovi de a n ove r a l l qua l i t a t i -
ve a nd qua nt i t a t i ve s ur ve y of a l l t he f or mi ng r e a c t i on
pr oduc t s . The a ddi t i on e s t e r i f i c a t i on i s f ol l owe d by
e t he r i f i c a t i on a nd c onde ns a t i on e s t e r i f i c a t i on a nd t he
ma i n r e a c t i on pr oduc t , monoe s t e r , i s di s pr opor t i ona t e d
yi e l di ng di e s t e r a nd di ol . I n a pol yf unc t i ona l s ys t e m,
t he l a t t e r r e a c t i on may c a us e s pl i t t i ng of t he pol yme r
c ha i n a nd f or ma t i on of ne w c r os s l i nks .
I nt r oduc t i on
The r e a c t i on be t we e n t he e poxi de a nd c a r boxyl
gr oups i s one of t he i mpor t a nt r e a c t i ons us e d i n c ur i ng
of e poxy r e s i ns . I t i s a l s o us e d i n t he pr e pa r a t i on of
uns a t ur a t e d pol ye s t e r s of t he a c r yl a t e or me t ha e r yl a t e
t ype . I n pa r t i c ul a r , howe ve r , t hi s r e a c t i on i s e mpl oye d
i n t he pr e pa r a t i on of c r os s l i nke d e l a s t ome r s f r om l i qui d
e a r boxyl - t e r mi na t e d t e l e c he l i c pol yme r s a nd pol ye poxi de s
(HOFFMAN a nd GOBRAN 1973). The ne t wor k pr ope r t i e s a r e
de t e r mi ne d by t he c ompos i t i on of t he s ys t e m, pr ope r t i e s
of t he i ni t i a l c ompone nt s , a nd ma i nl y by t he ne t wor k
s t r uc t ur e whi c h i s de pe nde nt on t he r e a c t i on me c ha ni s m.
Thi s i s why i t i s ne c e s s a r y t o know t he c our s e of t he
r e a c t i on a s a f unc t i on of t ke f unc t i ona l i t y a nd r e a c t i -
vi t y of t he i ni t i a l c ompounds a nd of t he i r mol a r r a t i o,
t ype a nd a mount of t he c a t a l ys t , t e mpe r a t ur e e t c . Due
t o t he c ompl i c a t e d c ompos i t i on of pr oduc t s i n pol yf unc -
t i ona l s ys t e ms , t he me c ha ni s m of t he c r os s l i nki ng r e -
a c t i on c a n pr e f e r a bl y be e xpl a i ne d t hr ough a s t udy of a
mode l s ys t e m r e pr e s e nt e d by monoe poxi de a nd monoc a r boni c
a c i d.
T h e m e c h a n i s m of the r e a c t i o n b e t w e e n e p o x i d e and
c a r b o x y l is r a t h e r c o m p l i c a t e d a n d h a s n o t y e t b e e n
f u l l y e l u c i d a t e d ( M A Y a n d T A N A K A 1973). G e n e r a l l y , the
r e a c t i o n p r o c e e d s t h r o u g h the a d d i t i o n of the c a r b o x y l
0170-0839/82/0007/0123/$01.20
124
t o t h e e p o x y g r o u p s w i t h f o r m a t i o n o f m o n o e s t e r . T h i s
a d d i t i o n e s t e r i f i c a t i o n i s u s u a l l y a c c o m p a n i e d b y s i d e
r e a c t i o n s . S H E C H T E R a n d W Y N S T R A ( 1 9 5 6 ) c o n s i d e r t h e
f o l l o w i n g f o u r r e a c t i o n s :
I ) e p o x i d e + a c i d - - ~ m o n o e s t e r ( a d d i t i o n e s t e r i f i c a t i o n )
2) e p o x i d e + m o n o e s t e r - - ~ e t h e r ( e t h e r i f i c a t i o n )
J) a c i d + m o n o e s t e r - - ~ d i e s t e r + w a t e r ( c o n d e n s a t i o n
e s t e r i f i c a t i o n )
4) e p o x i d e + w a t e r - - ~ g l y c o l ( h y d r o l y s i s )
I n t h e r e a c t i o n o f c a r b o x y l t e r m i n a t e d t e l e c h e l i c
p o l y m e r s w i t h p o l y f u n c t i o n a l e p o x i d e s , t h e a d d i t i o n
e s t e r i f i e a t i o n l e a d s to c h a i n e x t e n s i o n , w h i l e e t h e r i f i -
c a t i o n a n d c o n d e n s a t i o n e s t e r i f i c a t i o n c a u s e b r a n c h i n g
a n d c r o s s l i n k i n g . T h e r e l a t i v e r a t e of the f i r s t t w o
r e a c t i o n s d e c i d e s a b o u t t h e n e t w o r k d e n s i t y , a n d t h u s
a l s o a b o u t t h e m e c h a n i c a l p r o p e r t i e s o f t h e p r o d u c t
( c o n d e n s a t i o n e s t e r i f i c a t i o n is n e g l i g i b l y s l o w w i t h
r e s p e c t to t h e s e r e a c t i o n s ) .
W i t h a n a i m to v e r i f y t h e r e a c t i o n s c h e m e g i v e n
a b o v e u n d e r t h e c o n d i t i o n s of b a s e c a t a l y s i s , a n d
e s p e c i a l l y i n o r d e r to d e t e r m i n e t h e r e l a t i v e s i g n i f i -
c a n c e o f r e a c t i o n s l e a d i n g to c h a i n e x t e n s i o n , f o r m a t i o n
o f c r o s s l i n k s o r c h a i n s p l i t t i n g , w e i n v e s t i g a t e d t h e
b a s e - c a t a l y z e d ( t r i e t h y l a m i n e ) r e a c t i o n b e t w e e n e p o x i d e
a n d c a r b o x y l u s i n g a s i m p l e m o d e l s y s t e m p h e n y l g l y c i d y l
e t h e r - e a p r o i c a c i d .
E x p e r i m e n t a l
C h e m i c a l s . C a p r o i c a c i d (CA) a n d p h e n y l g l y c i d y l
e t h e r ( P G E ) w e r e d i s t i l l e d a t r e d u c e d p r e s s u r e a n d t h e i r
p u r i t y w a s determined b y g a s chromatography - 9 9 . 7 % C A )
a n d 9 9 . 6 % ( P G E ) . Triethylamine ( T E A ) w a s b o i l e d w i t h
a e e t a n h y d r i d e a n d r e d i s t i l l e d (b.p. J 6 0 K).
C h r o m i u m ( I I I ) c o m p l e x of d i i s o p r o p y l s a l i c y l i c a c i d
(M n = 2 8 0 0 - V P 0 , 1 0 w t . % C r ) w a s s u p p l i e d b y c o u r t e s y of
Dr. K l l s e k , I n s t i t u t e of C h e m i c a l T e c h n o l o g y , G o t t w a l d o v .
1-Phenyloxypropanediol-J-eaproate ( m o n o e s t e r - M ) w a s
s e p a r a t e d u s i n g a g e l c h r o m a t o g r a p h f r o m t h e r e a c t i o n
mixture p r e p a r e d by h e a t i n g o f e q u i m o l a r a m o u n t s o f I~3E
w i t h C A a n d 3 . 7 w t . % T E A at 3 7 3 K f o r o n e h o u r .
1-Phenyloxypropanediol-2,J-dicaproate ( d i e s t e r - D )
w a s o b t a i n e d s i m i l a r l y b y G P C s e p a r a t i o n from t h e r e -
a c t i o n m i x t u r e P G E : C A = I : 2 h e a t e d at 3 8 3 K f o r 8 h.
1-Phenyloxypropanediol ( g l y c o l - G ) w a s prepared b y
h y d r o l y s i s o f P G E i n a c e t i c a c i d i n t h e p r e s e n c e o f T E A
a n d s u l p h u r i c a c i d . T h e r e a c t i o n m i x t u r e ( 1 0 m l P G E ,
J 0 m l C H j C 0 0 H , 2 0 m l H 2 0 , 2 m l T E A a n d 0 . 5 m l H 2 S 0 4 ) w a s
h e a t e d a ~ 3 8 9 K f o r 8 h . T h e p r o d u c t w a s recrystallized
f r o m a m i x t u r e C H 2 C I 2 - h e x a n e ( m . p . J 2 9 K ) . T h e c o m p o s i -
t i o n a n d p u r i t y of t h e m o n o e s t e r , d i e s t e r a n d g l y c o l
w e r e c h e c k e d by G P C a n a l y s i s a n d m a s s s p e c t r o m e t r y .
1 2 5
A n a l y s i s . The r e a c t i o n m i x t u r e s w e r e a n a l y z e d u s i n g G P C
and the p r o d u c t s w e r e i d e n t i f i e d by m a s s s p e c t r o s c o p y .
G P C a n a l y s i s w a s c a r r i e d out on a gel c h r o m a t o g r a p h
w i t h five columns, 8 x 1 2 0 0 m m in size, p a c k e d w i t h the
s t y r e n e - d i v i n y l b e n z e n e c o p o l y m e r S-Gel 832 (Institute of
M a c r o m o l e c u l a r Chemistry, C z e c h o s l o v a k A c a d e m y of S c i e n -
ces). T e t r a h y d r o f u r a n was used as the e l u t i o n agent;
the q u a l i t a t i v e and q u a n t i t a t i v e c a l i b r a t i o n was perfor~n-
ed w i t h pure standards. W i t h o l i g o m e r i c ethers, only
q u a l i t a t i v e results w e r e o b t a i n e d by this method, b e c a u -
se the r e s p e c t i v e e l u t i o n peaks are not s u f f i c i e n t l y
separated. A n example of s e p a r a t i o n of the r e a c t i o n
m i x t u r e is g i v e n in Fig.1.
75'0 75.0
4~
600
840
J650
Fig.1. G P C r e c o r d of the r e a c t i o n m i x t u r e p h e n y l g l y c i d y l
e t h e r - c a p r o i c a c i d (T=358 K)
e l u t i o n volttmes (counts): p h e n y l g l y c i d y l e t h e r 84.0,
e a p r o i c a c i d 75.0, g l y c o l 72.0, m o n o e s t e r 68.0, d i e s t e r
65.0, e t h e r s 62.5; 60.6 a n d 58.8
M a s s s p e c t r a of the r e a c t i o n p r o d u c t s w e r e o b t a i n e d
u s i n g an M S - 9 0 2 m a s s s p e c t r o m e t e r at the ion source tem-
p e r a t u r e 413 K, e l e c t r o n e m i s s i o n 500 ~ A and e n e r g y 7 0 e ~
The m e t h o d was used in p a r t i c u l a r in the d e t e r m i n a t i o n
of m o n o e s t e r and d i e s t e r w h i c h are c h a r a c t e r i z e d by mo-
l e c u l a r ions w i t h the r e s p e c t i v e m a s s n u m b e r s m/e 266
and 364 and by the i n t e n s i v e lines of f r a g m e n t s a f t e r
the s p l i t t i n g - o f f of the p h e n y l o x y g r o u p at m / e = 173
a n d 271.
R e s u l t s and D i s c u s s i o n
W h e n s t u d y i n g the r e a c t i o n b e t w e e n p h e n y l g l y c i d y l
e t h e r (PGE) and c a p r o i c a c i d (CA), base c a t a l y z e d by
t r i e t h y l a m i n e (TEA), we f o u n d t h a t - as e x p e c t e d - the
a d d i t i o n of the c a r b o x y l to the epoxy g r o u p ( a d d i t i o n
e s t e r i f i c a t i o n ) is m a r k e d l y p r e f e r r e d , g i v i n g rise to
1 - p h e n y l o x y p r o p a n e d i o l - 3 - c a p r o a t e (monoester-M):
eric + ( ~ L H ~ O C H Q H - C H o 0 C 0 ( C H o ) ~ C H ~ ( i
)
126
In the i n i t i a l stage, i n d e p e n d e n t l y of the P G E to CA
m o l a r ratio, the a d d i t i o n e s t e r i f i c a t i o n is the only re-
a c t i o n o c c u r i n g in the system. B o t h r e a c t i o n c o m p o n e n t s
are c o n s u m e d at the same rate, and the m o n e e s t e r is the
only r e a c t i o n p r o d u c t (cf. Fig.2a-c).
80
60
r
20
8O
C
wtQ/,
S~
40
t" T - - - ~
G
4
I 2
t,h
t,h
b
t , h
" T " l ' I !
3 ~
t
1 2
t , h
e0
60
/,0
20
F i g . 2 The c h a n g e in the c o n c e n t r a t i o n of r e a c t i o n com-
p o n e n t s in the r e a c t i o n b e t w e e n p h e n y l g l y c i d y l e t h e r
and caproic acid
I PGE, 2 CA, 3 M, 4 D, 5 G, 6 ethers
2a: m o l a r ratio P G E : C A = 2 . 1 , c a t a l y s i s T E A (4.6 wt.-~),
T = 3 5 8 K
2b: m o l a r ratio P G E : C A = I : 2 , T E A (4.9 w t . - % ) , T = 3 5 8 K
2c: m o l a r ratio P G E : C A = I : I , T E A (3.7 wt.-~), T = ~ 7 ~ K
2d: m o l a r ratio P G E : C A = 2 : I , c a t a l y s i s c h r o m i u m iIII)
c o m p l e x of d i i s o p r o p y l s a l i c y l i c a c i d (I~t.%), T = 9 5 8 K
In the f u r t h e r stage, the r e a c t i o n c o u r s e d e p e n d s
on the m o l a r ratio of the i n i t i a l components. W i t h P G E
in excess, o l i g o m e r i c ethers are f o r m e d in the r e a c t i o n
m i x t u r e a f t e ~ the a c i d has b e e n c o n s u m e d - r e a c t i o n (2)
(Fig.2a). W i t h CA in excess a f t e r P G E has d i s a p p e a r e d ,
the a c i d r e a c t s w i t h the m o n o e s t e r w i t h f o r m a t i o n of
1-phenyloxypropanediol-2,5-dicaproate (diester-D) - con-
d e n s a t i o n esterification-reaetion (9) (Fig.2b ~.
D i e s t e r is also f o r m e d by r e a c t i o n (4 i d e s c r i b e d ' b e l o w :
127
+ .
O H 0
< ~ O C H ~ C H C H ~ O C O ( C H ~ ) ~ C H ~
0 ( C H 2 7 H C H 2 0 - ~ ) n
O H
~ 0 C H 2 ~ H C H 2 0 C 0 ( C H 2 ) 4 C H 3 + H 0 0 C ( C H 2 ) 4 C H 3
O H
( 2 )
< 0 C H 2 H C 2 0 C O ( C 2 ) 4 C H 3
OCO(CH2)4CH 3
( 3 )
T h e m o n o e s t e r content (Figs 2 a , b ) r e a c h e s a m a x i -
m u m d u r i n g the r e a c t i o n a n d t h e n d e c r e a s e s as a r e s u l t
of the c o n s e c u t i v e r e a c t i o n m e n t i o n e d a b o v e - e t h e r i f i -
c a t i o n or c o n d e n s a t i o n e s t e r i f i c a t i o n . F i g . 2 c shows,
h o w e v e r , that a l s o in a n e q u i m o l a r m i x t u r e the m o n o -
e s t e r c o n c e n t r a t i o n p a s s e s t h r o u g h a m a x i m u m d u r i n g the
r e a c t i o n . We f o u n d that in t h i s c a s e the loss of m o n o -
e s t e r w a s d u e to its d i s p r o p o r t i o n a t i o n to d i e s t e r a n d
1 - p h e n y l o x y p r o p a n e d i o l ( g l y c o l - G ) (4)
2 < o c H 2 H c 2 o c o ( c H 2 ) 4 c 3
o H (4)
~ 0 C H 2 7 H C H 2 0 C 0 ( C H 2 ) 4 C H 3
O C 0 ( C H 2 ) 4 C H 3
+ ~OCH27HCH20H
OH
B o t h t h e s e c o m p o u n d s w e r e i d e n t i f i e d in the r e a c t i o n
m i x t u r e by m e a n s of G P C a n d m a s s s p e c t r o m e t r y . T h e m a s s
s p e c t r a of the r e s p e c t i v e f r a c t i o n s i s o l a t e d by G P C
c o n t a i n m o l e c u l a r ions, a n d t h e i r t o t a l f r a g m e n t a t i o n
c o r r e s p o n d s to the m o n o e s t e r a n d g l y c o l .
F i g s 2 a - c s h o w that in the b a s e - c a t a l y z e d r e a c t i o n
b e t w e e n P G E a n d CA, b o t h e t h e r i f i c a t i o n a n d d i s p r o p o r -
t i o n a t i o n b e c o m e o p e r a t i v e o n l y a f t e r the a c i d has r e -
a c t e d , e v e n w i t h P G E p r e s e n t in e x c e s s . T h e e f f e c t of
the c a t a l y s t t y p e - T ~ A a n d the c h r o m i u m ( I I I ) c o m p l e x
of d i i s o p r o p y l s a l i c y l i c a c i d - on the c o u r s e c a n be sema
f r o m F i g s 2a,2d. T h e c h r o m i u m ( I I I ) c a t a l y s t is o b v i o u s l y
v e r y s e l e c t i v e f o r the a d d i t i o n e s t e r i f i c a t i o n , b e c a u s e
e t h e r i f i c a t i o n or d i s p r o p o r t i o n a t i o n has n o t b e e n o b -
s e r v e d e v e n a f t e r all the a c i d h a d b e e n c o n s u m e d .
U s i n g t h e s e r e s u l t s , the r e a c t i o n s c h e m e g i v e n
128
a b o v e m u s t be s u p p l e m e n t e d by the d i s p r o p o r t i o n a t i o n
r e a c t i o n :
m o n o e s t e r 9 d i e s t e r + g l y c o l
T h e r e f o r e , the r e a c t i o n of P G E a n d CA w i t h g l y c o l
l e a d i n g to the f o r m a t i o n of e t h e r s , or of m o n o e s t e r a n d
w a t e r s h o u l d a l s o be c o n s i d e r e d .
C o n c l u s i o n
A n i n v e s t i g a t i o n of the m o d e l r e a c t i o n h a s d e -
m o n s t r a t e d that only a d d i t i o n e s t e r i f i c a t i o n p r o c e e d s
in the i n i t i a l s t a g e in a b a s e - c a t a l y z e d s y s t e m .
F u r t h e r r e a c t i o n s - e t h e r i f i c a t i o n , c o n d e n s a t i o n e s t e r ~
f i c a t i o n , a n d d i s p r o p o r t i o n a t i o n are c o n s e C u t i v e a n d
b e c o m e o p e r a t i v e only a f t e r the a c i d or e p o x i d e h a s been
c o n s u m e d ; of these, e t h e r i f i c a t i o n is the f a s t e s t .
W h i l e e t h e r i f i c a t i o n a n d c o n d e n s a t i o n e s t e r i f i c a t i o n
r e q u i r e the p r e s e n c e of u n r e a c t e d e p o x i d e or c a r b o x y l
g r o u p s , d i s p r o p o r t i o n a t i o n p r o c e e d s a l s o a f t e r t h e s e
g r o u p s h a v e b e e n c o n s u m e d . I n a p o l y f u n c t i o n a l system,
this r e a c t i o n m a y s i g n i f i c a n t l y a f f e c t the n e t w o r k
s t r u c t u r e ( h e t e r o g e n e i t y ) by s i m u l t a n e o u s l y b r e a k i n g
the c h a i n s a n d g i v i n g rise to n e w c r o s s l i n k s .
R e f e r e n c e s
H O F F M A N , R . F . a n d G O B R A N , R . H . , R u b b e r Chem. T e c h n o l . 466,
1 3 9 (1973)
M A Y , C . A . a n d T A N A K A , Y . : E p o x y R e s i n s . C h e m i s t r y a n d
T e c h n o l o g y , N e w Y o r k : M . D e k k e r 1 9 7 3
SHECHTER',L. a n d W Y N S T R A , J . : I n d . E n g . Chem. 4_88, 86 (1956)
Received March 12, accepted March 16, 1982