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[ 5 4 ] EPOXY COMPOSITION CONTAINING ACID.ANIIYDRIDE COMPOUND OBTAINEDFROM NADIC METHYL ANI-IYDRIDE

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[ 7 3 ] A s s i g n e e : C a n a d i a n P a t e n t s a n d D e v e l o p m e ntL i m i t e d , O t t a w a , CanadaD e c . 1 8 , 1 9 7 3

[ 2 1 ] A p p l . N o . 2 4 2 5 , 8 1 3[ 5 2 ] US. Cl . . . . . . . . . . . . . . . . . . . . . . . . . . . 260/47 EA; 428/263;

4 2 8 / 2 6 8 ; 2 6 0 / 5 9 E P ; 2 6 0 / 8 3 6 ; 2 6 0 / 8 3 7 R[51] I n t . C 1 . 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C08G 30/12[ 5 8 ] F i e l d o f Search . . . . . . . . . 260/47 EA, 5 9 , 78.4 EP,

2 6 0 / 7 5 E P , 3 4 6 . 6 , 8 3 6 , 8 3 7[ 5 6 ] R e f e r e n c e s C i t e d

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P r i m a r y E x a m i n e r - M u r r a y T i l l m a nA s s i s t a n t E x a m i n e r - T . P e r t i l l aA t t o r n e y , A g e n t , o r F i r m - C h r i s t e n & a b o l[ 5 7 ] ABSTRACTNew e p o x y r e s i n s a r e d e s c r i b e d h a v i n g h i g h s t r e n g t hand d u c t i l i t y . The n o v e l f e a t u r e o f t h e s e new r e s i n s i st h a t a normal epoxy r e s i n component i s c r o s s - l i n k e dw i t h a n o v e l m i x t u r e o f m e t h y l e n d o m e t h y l e n e t e t r ah y d r o p h t h a l i c a c i d a n d m e t h y l e n d o m e t h y l e n e t e t r ah y d r o p h t h a l i c a n h y d r i d e . An a d d i t i o n a l u s u a l a n h yd r i d e , e . g . p h t h a l i c a n h y d r i d e , may a l s o b e p r e s e n t .The p r o d u c t s a r e e x c e l l e n t e l e c t r i c a l i n s u l a t o r s anda r e s u i t a b l e f o r c a s t i n g , vacuum ? l l i n g , l a m i n a t i n g ,b i n d i n g , e t c .

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3 , 9 5 7 , 7 2 71EPOXY COMP OSITION CONTAINING ACIDANI-IYDRIDE COMPOUND OBTAINED FROMNADIC METHYL ANHYDRIDEBACKGROUND OF THE INVENTION

1 . F i e l d o f t h e I n v e n t i o nT h i s i n v e n t i o n r e l a t e s t o epoxy r e s i n s a n d , mor e p a rt i c u l a r l y , t o e p o x y r e s i n s o f i m p r o v e d s t r e n g t h a n dd u c t i l i t y .2 . D e s c r i p t i o n o f t h e P r i o r A r t

R e s i n s known a s epoxy r e s i n s have r e c e i v e d widei n d u s t r i a l a c c e p t a n c e and a r e u s e d f o r m an y d i f f e r e n tp u r p o s e s . The epoxy r e s i n s t h e m s e l v e s a r e p e r m a n e n t l yt h e r m o p l a s t i c a n d r e q u i r e t h e a d d i t i o n o f c r o s s - l i n k i n ga g e n t s o r o t h e r r e a c t i v e m a t e r i a l s i n o r d e r t h a t t h e ymay b e c u r e d t o h a r d , i n f u s i b l e r e s i n o u s p r o d u c t s .However d e s i r a b l e a s t h e y may b e , t h e c u r e d e p o x yp r o d u c t s h a v e a s e r i o u s d i s a d v a n t a g e i n t h a t t h e y a r ei n h e r e n t l y b r i t t l e . T h i s l a c k o f ? e x i b i l i t y h a s r e s t r i c t e dtheir u se in many areas.I t i s a l s o k n o w n , e . g . i n G o l d b e r g e t a l US. P a t . N o .3 , 3 8 8 , 1 8 5 p a t e n t e d J u n e 1 1 , 1 9 6 8 t h a t t h e p r o p e r t i e so f e p o x y r e s i n s c a n b e i m p r o v e d b y b l e n d i n g t h e r e s i nw i t h a p o l y f u n c t i o n a l a n h y d r i d e c u r i n g a g e n t .The G r u e n w a l d US. P a t . N o . 3 , 3 9 6 , 1 4 5 p a t e n t e dA u g . 6 , 1 9 6 8 a l s o d e s c r i b e s c u r i n g a g e n t s f o r e p o x yr e s i n s i n c l u d i n g l o n g c h a i n p o l y f u n c t i o n a l a l i p h a t i ca c i d s o r a n h y d r i d e s . T h e s e a r e i n t e n d e d f o r i m p r o v i n gt h e e l a s t i c i t y o f t h e c u r e d r e s i n .

H o w e v e r , t h e p r e s e n t i n v e n t o r s f o u n d t h a t a l t h o u g he p o x y r e s i n s c r o s s - l i n k e d w i t h a n h y d r i d e s h a d i mp r o v e d t e n s i l e s t r e n g t h , t h e r e s i n s e x h i b i t e d a b r i t t l ef r a c t u r e w i t h a q u i t e l o w s t r a i n a t f a i l u r e }The o b j e c t o f t h e p r e s e n t i n v e n t i o n i s t o p r o v i d e a ni m p r o v e d c r o s s - l i n k e d e p o x y r e s i n h a v i n g h i g h t e n s i l es t r e n g t h , h i g h e l o n g a t i o n , d u c t i l i t y , h i g h i n t e r l a m i n a rs h e a r s t r e n g t h , g o o d p r o c e s s a b i l i t y a n d l o w c o s t .

SUMMARY OFTHE INVENTIONA c c o r d i n g t o one f e a t u r e o f t h e p r e s e n t i n v e n t i o n , ani m p r o v e d e p o x y r e s i n h a s b e e n d e v e l o p e d i n w h i c h t h e

epoxy r e s i n component i s c r o s s - l i n k e d w i t h a m i x t u r eo f m e t h y l e n d o m e t h y l e n e t e t r a h y d r o p h t h a l i c a c i d a n dm e t h y l e n d o m e t h y l e n e t e t r a h y d r o p h t h a l i c a n h y d r i d e .I t h a s s u r p r i s i n g l y b e e n f o u n d t h a t t h e a d d i t i o n o f t h i sm i x t u r e p r o v i d e s m a j o r i m p r o v e m e n t s i n t e n s i l es t r e n g t h a n d e l o n g a t i o n a t f a i l u r e i n t h e c u r e d e p o x yresin.M e t h y l e n d o m e t h y l e n e t e t r a h y d r o p h t h a l i c a n h y d r i d ei s c o m m o n l y known a s N a d i c m e t h y l a n h y d r i d e(NMA) nd s a low v i s c o s i t y l i q u i d o f about 250 c p s a troom t e m p e r a t u r e . I t i s a v e r y p o p u l a r a n h y d r i d e f o re p i d e r e a c t i v e c o m p o s i t i o n s b e c a u s e i t i s a l i q u i d t h a tc a n b e e a s i l y i n c o r p o r a t e d i n t o t h e r e s i n a n d g i v e sp r o d u c t s w i t h h i g h h e a t d i s t o r t i o n t e m p e r a t u r e s . M o s ta n h y d r i d e s c a n b e c o n v e r t e d t o t h e a c i d b y h y d r o l y s i sb u t t h e y a r e g e n e r a l l y n o t u s e f u l i n t h e e p o x y r e s i nt e c h n o l o g y .However, i n t h i s i n v e n t i o n i t h a s b e e n f o u n d t h a t as p e c i a l a c i d - a n h y d r i d e compound w h i c h i s a m i x t u r e o fm e t h y l e n d o m e t h y l e n e t e t r a h y d r o p h t h a l i c a c i d a n dm e t h y l e n d o m e t h y l e n e t e t r a h y d r o p h t h a l i c a n h y d r i d e i su n i q u e l y e f f e c t i v e a s a c r o s s - l i n k i n g a g e n t f o r e p o x i e s .

T h i s s p e c i a l compound w i l l b e r e f e r r e d t o h e r e i n a f t e ra s t h e NMA c i d - a n h y d r i d e compound.The NMA c i d - a n h y d r i d e compound i s i t s e l f a newm a t e r i a l a n d r e p r e s e n t s a n o t h e r f e a t u r e o f t h e p r e s e n t

i n v e n t i o n . I t c a n r e a d i l y j b e p r o d u c e d b y h e a t i n g m e t h y le n d o m e t h y l e n e t e t r a h y d r o p h t h a l i c a n h y d r i d e w i t h ac o n t r o l l e d a mou nt o f w a t e r . The s t o i c h i o m e t r i camount o f w a t e r i s s e l e c t e d f o r t h e d e s i r e d a n h y d r i d e5 a c i d r a t i o a n d t h i s r a t i o w i l l n o r m a l l y b e a t l e a s t 1 , s i n c efrom a t h e o r e t i c a l p o i n t o f view t h i s i s t h e l o w e s t r a t i o

20

25

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t h a t c a n b e u s e d w i t h t h e r e s i n w i t h o u t w a t e r b e i n gformed i n t h e r e a c t i o n . The u p p e r l i m i t o f t h e r a t i o i sn o t c r i t i c a l , b u t l i t t l e b e n e f i t i s o b t a i n e d w i t h a r a t i o o fa n h y d r i d e / a c i d a b o v e a b o u t 1 2 . The p r e f e r r e d r a t i or a n g e f o r c o m m e r c i a l p r o c e s s e s i s a b o u t 3 t o 1 0 . Thel o w r a t i o s g i v e t h i c k , s t i c k y o r s o l i d w h i t e c r y s t a l l i n em a t e r i a l s w h i l e t h e h i g h e r r a t i o s g i v e l o w v i s c o s i t y honey colour ?uids. _The w a t e r ' s h o u l d b e r e t a i n e d i n t h e s y s t e m u n t i l t h er e a c t i o n s a r e c o m p l e t e a n d t h e p r o c e s s i n g t e m p e r a t u r ei s s e l e c t e d t o e n s u r e c o n v e r s i o n i n a r e a s o n a b l e l e n g t ho f t i m e . F o r e x a m p l e , b y m i x i n g 4 0 p a r t s m e t h y l e nd o m e t h y l e n e t e t r a h y d r o p h t h a l i c a n h y d r i d e w i t h 1 p a r tw a t e r , h e a t i n g t o 8 5 C a n d m a i n t a i n i n g t h i s f o r 1 1 / 2h o u r s , a n NMA c i d - a n h y d r i d e compound s o b t a i n e dh a v i n g a n a n h y d r i d e t o a c i d , r a t i o o f 2 . 2 5 : 1 .

The p r e s e n t i n v e n t i o n can be a p p l i e d t o a wide rangeo f e p o x y r e s i n s i n c l u d i n g d i g l y c i d y l e t h e r o f b i s - p h e n o lA , e . g . Epon 8 2 8 a v a i l a b l e f r o m S h e l l C h e m i c a l C o . ,e p o x i d i z e d n o v o l a c r e s i n s , e . g . DEN 3 1 a v a i l a b l e f r o mDow C h e m i c a l C o . , c y c l i c a l i p h a t i c e p o x y r e s i n s , e . g .ERL 4 2 8 9 a v a i l a b l e f r o m U n i o n C a r b i d e C o r p . , e t c .I n o r d e r t o o p t i m i z e t e n s i l e s t r e n g t h p r o p e r t i e s , t h ec r o s s - l i n k i n g a g e n t i s n o r m a l l y used i n a c o n c e n t r a t i o no f a b o u t 5 0 t o 1 5 0 p a r t s p e r h u n d r e d r e s i n ( p h r ) . Con

. c e n t r a t i o n o u t s i d e t h i s r a n g e m ay b e p o s s i b l e depend

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i n g on t h e r e s i n u s e d . With a n o v o l a c r e s i n h a v i n g ane q u i v a l e n t w e i g h t o f 1 7 5 , v e r y g o o d p r o p e r t i e s w e r eo b t a i n e d a t a c o n c e n t r a t i o n o f 80 t o 1 0 5 p h r , w i t h t h eb e s t v a l u e s a t a b o u t 90 t o 9 5 p h r . The a d d i t i o n o f o t h e ra n h y d r i d e s h a s a b e n e ? c i a l e f f e c t on t e n s i l e p r o p e r t i e sp r o v i d e d t h e t o t a l c o n c e n t r a t i o n o f t h e c r o s s - l i n k i n ga g e n t s r e m a i n s w i t h i n t h e a b o v e r a n g e . Among t h eo t h e r a n h y d r i d e s t h e r e c a n b e mentioned a r e p h t h a l i ca n h y d r i d e , t e t r a h y d r o p h t h a l i c a n h y d r i d e , h e x a h y d r op h t h a l i c a n h y d r i d e , s u c c i n i c a n h y d r i d e , d o d e c e n y l s u cc i n i c a n h y d r i d e a n d m e t h y l N a d i c a n h y d r i d e . I n t e r m so f c o s t a n d e f f e c t i v e n e s s t h e p h t h a l i c a n h y d r i d e i s p a rt i c u l a r l y d e s i r a b l e . W h i l e t h e s e a d d i t i o n a l a n h y d r i d e sh a v e a b e n e ? c i a l e f f e c t , i t must b e a p p r e c i a t e d t h a t t h eNMA c i d - a n h y d r i d e c o m p o u n d b y i t s e l f p r o d u c e s a ne x c e l l e n t p r o d u c t which c a n ?nd m a ny p r a c t i c a l u s e s .A a t a l y s t i s r e q u i r e d t o o p e n t h e a n h y d r i d e r i n g s ot h a t u n i o n c a n t a k e p l a c e w i t h t h e e p o x y a n d h y d r o x y lg r o u p s p r e s e n t s T h e r e a r e s e v e r a l methods a v a i l a b l e f o ri n t r o d u c i n g a c a t a l y s t i n t o t h e s y s t e m . T h e s e i n c l u d e :a . p r e a c t i v a t i o n - o f t h e r e s i nb . p r e a c t i v a t i o n o f t h e c r o s s l i n k i n g a g e n t0 . a d d i t i o n o f c a t a l y s t d u r i n g o r a f t e r m i x i n g o f t h eingredients , d . a d d i t i o n o f l a t e n t c a t a l y s t t o t h e c o m p o s i t i o n .A e r t i a r y a m i n e c a t a l y s t i s p a r t i c u l a r l y s a t i s f a c t o r yand t i s u s u a l l y u s e d i n amounts o f a b o u t 0.1% t o 0.5%based on t h e r e s i n .T h e e p o x y r e s i n , NMA c i d - a n h y d r i d e c o m p o u n d ,a d d i t i o n a l a n h y d r i d e and c a t a l y s t c a n a l l b e mixedt o g e t h e r a s a s i n g l e c u r a b l e c o m p o s i t i o n . The NMAa c i d - a n h y d r i d e c o m p o u n d m i x e s r e a d i l y w i t h t h e r e s i na t room t e m p e r a t u r e a n d t h e a d d i t i o n a l a n h y d r i d e( p h t h a l i c a n h y d r i d e ) d i s s o l v e s a s t h e m i x t u r e i s s l o w l yh e a t e d w i t h s t i r r i n g t o ' a b o u t 1 0 0 C . F o r l a r g e b a t c h e s ,i t h a s b e e n f o u n d c o n v e n i e n t t o a d d p h t h a l i c a n h y d r i d e

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3 , 9 5 7 , 7 2 73t o a p r e h e a t e d m i x t u r e o f r e s i n and NMA c i d - a n h yd r i d e compound w h e r e s o l u t i o n i s r a p i d a t a b o u t 8 0 C .Lower t e m p e r a t u r e s may b e u s e d b u t l o n g e r t i m e s a r et h e n r e q u i r e d t o d i s s o l v e t h e p h t h a l i c a n h y d r i d e .The c u r i n g p r o c e s s i s i m p o r t a n t s i n c e h i g h s t r e n g t ha n d d u c t i l i t y a r e g e n e r a l l y o b t a i n e d w i t h v e r y c a r e f u l l yc o n t r o l l e d h e a t i n g . P r e f e r a b l y a ? r s t s t a g e c u r e i s cond u c t e d a t l o w t e m p e r a t u r e s f o r l o n g t i m e s f o l l o w e d b yp o s t c u r i n g a t e l e v a t e d t e m p e r a t u r e s t o c o m p l e t e c r o s sl i n k i n g . The n i t i a l c u r e i s p r e f e r a b l y m a d e a t a tempera t u r e o f 9 0 t o 120C f o r a p e r i o d o f t o 24 h o u r s , mostp r e f e r a b l y a t about 9 0 t o 110C f o r 2 t o 6 h o u r s .S h o r t e r t i m e s a r e matched w i t h h i g h e r t e m p e r a t u r e sw h i l e l o n g e r t i m e s a t t h e i n i t i a l t e m p e r a t u r e s r e d u c e ss h r i n k a g e a n d g i v e s i n c r e a s e d e l o n g a t i o n . T h e r e i s at e n d e n c y f o r t h e c o m p o s i t i o n t o g e l a t t h i s s t a g e .The ? n a l c u r e t e m p e r a t u r e i s h i g h e r , hence t h e molec u l e s b eco m e more mobile and a l l r e a c t i o n s can bec o m p l e t e d . I t i s u s u a l l y c o n d u c t e d a t a t e m p e r a t u r e o fa b o u t 1 5 0 l 75C f o r a p e r i o d o f 6 t o 8 h o u r s . Thereaft e r , t h e p r o d u c t i s a l l o w e d t o c o o l s l o w l y , u s u a l l y o v e ra p e r i o d o f a b o u t 8 h o u r s , t o h a n d l i n g t e m p e r a t u r eb e f o r e r e m o v a l , t o r e d u c e i n t e r n a l s t r e s s i n g .I t i s p a r t i c u l a r l y n o t e w o r t h y t h a t d u r i n g t h e p r e p a r at i o n s t a g e a c c o r d i n g t o t h i s i n v e n t i o n ( a n d u n l i k e p r e v io u s s y s t e m s ) t h e t e n d e n c y f o r p h t h a l i c a n h y d r i d e t of u m e o r s u b l i m a t e and condense o u t on c o o l e r p a r t s o ft h e p r o c e s s i n g e q u i p m e n t i s g r e a t l y r e d u c e d . The t e mp e r a t u r e a t w h i c h p h t h a l i c a n h y d r i d e p r e c i p i t a t e s i n ac o o l i n g m i x t u r e i s a l s o g r e a t l y r e d u c e d .The c u r i n g p r o c e s s i s b e l i e v e d t o p r o c e e d a c c o r d i n gt o t h e f o l l o w i n g e q u a t i o n :

4t h e c a t a l y s t and j o i n s t h e epoxy group t o g i v e a n e s t e rl i n k a g e and a n o t h e r a c t i v e h y d r o x y l g r o u p f o r m s .

I n t h e d r a w i n g s w h i c h i l l u s t r a t e t h e i n v e n t i o n :F I G . 1 shows t h e s t o i c h i o m e t r i c r e l a t i o n s h i p between

t h e epoxy r e a c t i v e compositions when i t c o n t a i n s twoc r o s s - l i n k i n g a g e n t s and a n o v o l a c r e s i n w i t h a n e q u i v al e n t w e i g h t o f 1 7 5 i . e . ( t h e NMA c i d - a n h y d r i d e comp o u n d , p h t h a l i c a n h y d r i d e a n d DEN 4 3 1 n o v o l a cr e s i n ) a n dFIG. 2 i s a s e r i e s o f s t r e s s - s t r a i n c u r v e s showing t h es u p e r i o r d u c t i l i t y o f t h e p r o d u c t s o f t h e i n v e n t i o n .

I n F I G . 1 , a t y p i c a l l i n e j o i n i n g 1 0 3 . 8 p h r a n d 8 4 . 6p h r i s i d e n t i ? e d a s t h e c a l c u l a t e d e q u i v a l e n c e l i n e f o ra n a c i d - a n h y d r i d e compound h a v i n g a n a n h y d r i d e : a c i dr a t i o o f : 1 . The 1 0 3 . 8 p h r s t h e q u a n t i t y o f a c i d - a n h yd r i d e compound a l o n e w h i c h w o u l d c o m p l e t e l y r e a c tw i t h t h e r e s i n , a n d t h e 8 4 . 6 p h r i s t h e q u a n t i t y o fp h t h a l i c a n h y d r i d e w h i c h a l o n e w o u l d r e a c t c o m p l e t e l yw i t h t h e r e s i n . Any p o i n t on t h i s l i n e e s t a b l i s h e s t h et h e o r e t i c a l q u a n t i t i e s o f a c i d - a n h y d r i d e c o m p o u n d a n dp h t h a l i c a n h y d r i d e t h a t a r e r e q u i r e d t o c o m p l e t e l yr e a c t w i t h t h e r e s i n . To t h e r i g h t o f t h i s e q u i v a l e n c el i n e a r e e x c e s s c r o s s - l i n k i n g a g e n t s (CLA) w h i l e t o t h el e f t t h e r e i s e x c e s s r e s i n . I n p r a c t i c e i t h a s been foundt h a t m a x i m u m s t r e n g t h l i e s on a l i n e t h a t d e v i a t e s fromt h i s e q u i v a l e n c e l i n e a s shown i n F I G . 1 a s m a x i m u ms t r e n g t h l i n e . L i n e s a r e a l s o i n c l u d e d f o r a n h y d r i d e :a c i d r a t i o s o f 2 . 5 : ] and 7 5 : 1 .

Thus, a s shown by t h e l i n e s on FIG. 1 , i f one u s e s 60p h r o f t h e NMA c i d - a n h y d r i d e compound h a v i n g a na n h y d r i d e : a c i d r a t i o o f 5 : 1 , t h e n 3 5 . 5 p h r o f p h t h a l i c

/ \ 1 0 i ? 9 / o \ / o \2 CH2CHCH2O o u t f i t - C H 2 - | - HO-C C-OH + 2 o=c c: =c c=oCH2 CH C H 3

5m ACID ANHYDRIDE PHTHALICANHYDRIDE

H E A T8 .

CATALYST

OH 0 0 O H on pi t C -0 H2-CHCH2Olu = CHo m C O 3c H g : C = Ol3 OH

The above e q u a t i o n shows a r e a c t i o n o f a n o v o l a cr e s i n w i t h t h e NMA a c i d - a n h y d r i d e compound a n dp h t h a l i c a n h y d r i d e . I n t h i s r e a c t i o n , t h e two c a r b o x y l i c 6 5a c i d g r o u p s o f t h e a c i d r e a c t w i t h two epoxy g r o u p s o ft h e n o v o l a c r e s i n f o r m i n g an e s t e r and new h y d r o x y lg r o u p s . Each a n h y d r i d e r i n g i s b r o k e n w i t h t h e a i d o f

I I I I IO C H 2 $ H C H 2 O C C O C H 2 C H C H 2 O o c H Z C H - C H 2 O - C E H E@ 0 4 2 6 H O - ( . C H 3@ 1 2 5NOTE:

t o E r e r e a c t i o ns i t e s ready t o co mp l e i e c r o s s l i n k i n gw i t h u d i u c e n t m o lecules

a n h y d r i d e i s t h e o r e t i c a l l y r e q u i r e d t o c o m p l e t e t h er e a c t i o n s w i t h t h e r e s i n .The p h y s i c a l p r o p e r t i e s o f t h e c o m p o s i t i o n s o f t h ei n v e n t i o n m a k e t h e m e x c e l l e n t candidates a s a matrixm a t e r i a l i n c o m p o s i t e s b e c a u s e t h e y a r e s t r o n g , d u c t i l ea n d h a v e g o o d e l o n g a t i o n a t f a i l u r e .

8/12/2019 NMA Water US3957727

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3 , 9 5 7 , 7 2 75O t h e r u s e s o f t h e c o m p o s i t i o n o f t h i s i n v e n t i o n i n

c l u d e vacuum ? l l i n g o f g l a s s f a b r i c f o l l o w e d b y c u r i n gi n a h e a t e d h y d r a u l i c p r e s s . F l a t , c u r v e d a n d compoundc u r v e d hardware a r e m a d e i n t h i s w a y .The c o m p o s i t i o n o f t h e i n v e n t i o n h a s a w i d e r a n g e o fp o t l i v e s d e p e n d i n g o n c a t a l y s i s l e v e l a n d t e m p e r a t u r ew h i c h p e r m i t s p r o p o r t i o n a l r a n g e s o f v i s c o s i t y s u i t a b l ef o r i m p r e g n a t i o n o f ? l a m e n t s , y a r n s , r o v i n g o r f a b r i c s ,f o r w e t w i n d i n g o p e r a t i o n o r f o r t h e p r e p a r a t i o n o fp r e p r e g s f o r s u b s e q u e n t t a i l o r i n g a n d p r o c e s s i n g b y v a c u u m pressing or autoclave c u r i n g . .The c o m p o s i t i o n c a n a l s o b e ? l l e d w i t h p r e c i p i t a t es i l i c o n d i o x i d e and can be used a s a m a t r i x f o r other? l l e r s or whiskers such a s mica p l a t e l e t s or s i l i c o n carb i d e .

T y p i c a l o f t h e p h y s i c a lp r o p e r t i e s a r e t h e f o l l o w i n g :T e n s i l e s t r e n g t hE l o n g a t i o n a t b r e a kD u c t i l e

15000 ~ 17000 lb/in8 - 10i l l u s t r a t e d b y t h e hook i n t h es t r e s s - s t r a i n curve of FIG. 2Modulus o f

e l a s t i c i t y 3 . 6 4 . 6 X 1 0 5 l b / i n 2Sh r inkage l 1.5%

I t h a s b e e n n o t e d t h a t g e n e r a l l y t h e r e i s l i t t l e c h a n g ei n e l o n g a t i o n o r m o d u l u s o f e l a s t i c i t y w i t h c h a n g e s i nc o m p o s i t i o n o r p r o c e s s i n g . H o w e v e r , b o t h t h e k i n d a n dq u a n t i t y o f a t a l y s t s h o w e d s u b s t a n t i a l c h a n g e s i n modu l u s .The t e n s i l e p r o p e r t i e s a r e s u b s t a n t i a l l y i m p r o v e d i nt h e p r o d u c t s o f t h i s i n v e n t i o n . As a p o i n t o f c o m p a r is o n , s i m i l a r p r o d u c t s w i t h c o m m o n epoxy r e s i n s anda n h y d r i d e s i n t h e c o n v e n t i o n a l manner o f t h e epoxytechnology have a t e n s i l e s t r e n g t h of 12,000 13,000p s i . W h e n t h e s e same r e s i n s a r e p r o c e s s e d a c c o r d i n g t ot h e p r e s e n t i n v e n t i o n t h e t e n s i l e s t r e n g t h s a r e i n c r e a s e dt o t h e l e v e l s shown n t h e t a b l e a b o v e , a l o n g w i t h b e t t e re l o n g a t i o n a t f a i l u r e a n d g o o d d u c t i l i t y .Y e t a n o t h e r a d v a n t a g e o f t h e c o m p o s i t i o n o f t h i si n v e n t i o n i s t h a t t h e exotherms a r e q u i t e low and cane a s i l y b e c o n t r o l l e d . T h i s i s i m p o r t a n t when a r g e i t e m sa r e b e i n g c o n s t r u c t e d .To l l u s t r a t e t h e manner i n w h i c h t h e i n v e n t i o n mayb e c a r r i e d o u t , t h e f o l l o w i n g e x a m p l e s a r e g i v e n . I t i s t ob e u n d e r s t o o d , h o w e v e r , t h a t t h e s e e x a m p l e s a r e f o rt h e p u r p o s e o f l l u s t r a t i o n and t h e i n v e n t i o n i s n o t t o ber e g a r d e d a s l i m i t e d t o any o f t h e s p e c i ? c c o n d i t i o n scited he re i n .

E x a m p l e 1 a . P r e - a c t i v a t i o n of the Epoxy ResinA DEN 3 1 n o v o l a c r e s i n was p r e - a c t i v a t e d b y d i ss o l v i n g 0 . 1 p a r t s o f d i e t h y l a r n i n e h y d r o c h l o r i d e i n _ 1 0 0

p a r t s o f t h e r e s i n . T h i s was h e a t e d a t 185C f o r about1 0 m i n u t e s and t h e n r a p i d l y c o o l e d t o r oo m temperat u r e . The p r e a c t i v a t e d r e s i n had a l o n g s h e l f l i f e andc o u l d b e s t o r e d a t room t e m p e r a t u r e f o r s e v e r a l w e e k s .b . P r e p a r a t i o n o f NMA c i d - a n h y d r i d e CompoundTo a h e a t i n g v e s s e l ? t t e d w i t h a condenser werea d d e d 8 0 0 p a r t s b y w e i g h t o f m e t h y l e n d o m e t h y l e n et e t r a h y d r o p h t h a l i c a n h y d r i d e , 2 0 p a r t s b y w e i g h t o fw a t e r a n d 0 . 2 p a r t s b y w e i g h t o f b e n z y l d i m e t h y l a m i n e(BDMA). T h i s was h e a t e d w i t h c o n s t a n t s t i r r i n g t o85C and m a i n t a i n e d a t t h i s t e m p e r a t u r e o f 1 1 / 2 h o u r s .An NMA c i d - a n h y d r i d e compound w a s o b t a i n e d h a vi n g a n a n h y d r i d e z a c i d r a t i o o f 2 . 2 5 : 1 .

6c . P r e p a r i n g C u r a b l e CompositionTo 1 0 0 p a r t s b y w e i g h t o f t h e p r e - a c t i v a t e d n o v o l a cr e s i n f r o m p a r t ( a ) w e r e v a d d e d 6 0 p a r t s b y w e i g h t o fNMA a c i d - a n h y d r i d e . c o m p o u n d , a n d 3 0 p a r t s b yw e i g h t o f p h t h a l i c f a n h y d r i d e . T h e a c i d c o m p o u n dm i x e d r e a d i l y w i t h t h e r e s i n a n d t h e p h t h a l i c a n h y d r i d e

d i s s o l v e d a s t h e m i x t u r e w a s h e a t e d , c o m p l e t e l y d i ss o l v i n g a t a b o u t 1 0 0 C . T h e m i x t u r e h a s a v i s c o s i t y o fa b o u t 6 0 0 0 ' c e n t i p o i s e s a t room t e m p e r a t u r e a n d a pp r o x i m a t e l y z e r o a t a b o u t 1 0 0 C . T h i s m a k e s t p o s s i b l et o u s e t h e m a t e r i a l i n c a s t i n g , p r e i m p r e g n a t i o n a n d w e tw i n d i n g w h i l e p o t l i f e c a n b e c o n t r o l l e d b y c o n c e n t r at i o n and t y p e o f c a t a l y s t a s w e l l a s t e m p e r a t u r e . When. h i g h e r v i s c o s i t i e s a r e d e s i r e d e i t h e r r e s i n s o f h i g h e rv i s c o s i t y a n d / o r . a c i d c o m p o u n d s h a v i n g h i g h e r v i s c o si t y may e used.

2 0 .

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40

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6 5

d . F o r m i n g a n d C u r i n g o f F u n c t i o n a l P a r tAn e l e c t r i c a l i n s u l a t o r w a s made b y c a s t i n g t h e s o l ut i o n o f p a r t ( c ) a r o u n d a c o p p e r t a b l e . T h i s s o l u t i o nwas p o u r e d i n t o a m o l d , p r e h e at e d t o 1 0 0 C and t h e nt h e t o t a l mass was cooled t o t h e cure temperature of9 5 C . This i n i t i a l c u r e was maintained a t 95C f o r 6h o u r s . The ? n a l c u r e was conducted a t 160C f o r 8h o u r s f o l l o w e d b y c o o l i n g a t room t e m p e r a t u r e d u r i n gan a d d i t i o n a l 8 h o u r s . The i n s u l a t o r formed was 28i n c h e s l o n g a n d c o n t a i n e d a p p r o x i m a t e l y 5 . 6 k g . o fmaterial.

E x a m p l e 2A e r i e s o f c u r a b l e r e s i n m i x e s w e r e p r e p a r e d f o rd e t e r m i n a t i o n o f t e n s i l e p r o p e r t i e s . An NMA a c i d

a n h y d r i d e compound was p r e p a r e d f o l l o w i n g t h e p r oc e d u r e o f E x a m p l e 1 ( b ) t o p r o v i d e a compound w i t ha n a n h y d r i d e 2 a c i d r a t i o o f 5 . 9 1 1 . V a r i o u s amounts o ft h i s was mixed w i t h 1 0 0 p a r t s DEN 31 n o v o l a c r e s i na n d v a r y i n g a m o u n t s o f p h t h a l i c a n h y d r i d e w a s a l s oadded t o some o f t h e samples a s s e t out i n Table 1 .Each r e s i n s a m p l e w a s c a t a l y z e d w i t h 0 . 2 5 p h r o f b e nz y l d i m e t h y l a m i n e a n d was h e a t e d w i t h s t i r r i n g t o a b o u t1 0 0 C t o f o r m a c l e a r y e l l o w i s h l i q u i d .The s a m p l e s w e r e made i n m o l d s c o n s i s t i n g o f twov e r t i c a l s t e e l p l a t e s , 1 l X 7 X / 2 i n . , t h a t were ground t oa ?ne ? n i s h o f a p p r o x i m a t e l y 20 m i c r o i n c h e s ands e p a r a t e d by a U-shaped m e t a l s p a c e r Vs i n c h t h i c k t oc o n t r o l t h e t h i c k n e s s . A i l i c o n e mold r e l e a s e (DOWN o . 2 0 ) was u s e d t o p o l i s h t h e mold components t o p r e v e n t a d h e s i o n o f t h e p l a s t i c t o t h e m e t a l .

Each c u r a b l e - I r e s i n o u s s a m p l e i n t h e f o r m o f a c l e a ry e l l o w i s h l i q u i d w a s p o u r e d i n t o t h e m o l d s p r e h e a t e dto 100c. ,Heat was p r o v i d e d b y a n a i r c i r c u l a t i n g oven t h a t h a st h e c a p a c i t y t o r a i s e t h e t e m p e r a t u r e f r o m 8 0 t o 200Ci n 2 0 m i n u t e s . Of c o u r s e , t h e t e m p e r a t u r e o f t h e moldl a g s t h e o v e n t e m p e r a t u r e d u r i n g t h e s e c o n d t e m p e r at u r e s t a g e .The s h e e t s were c u r e d w i t h two t e m p e r a t u r e s t a g e s .The ? r s t s t a g e was f o r 6 h o u r s a t 100C and t h e secondwas f o r 8 hours a t 1 6 0 C . The c a s t s h e e t s were cooleds l o w l y i n t h e o v e n , u s u a l l y o v e r n i g h t , u n t i l a h a n d l i n gtemperature was reached. The s h e e t s were then r emoved and marked f o r i d e n t i ? c a ti o n .

S t r i p s o f c a s t p l a s t i c were c u t on a h i g h s p e e d c u t t e rt o a s p e c i m e n s h a p e t h a t met ASTM D638-68 t y p e 1 1e x c e p t t h a t t h e g a u g e l e n g t h i s 1 i n c h . A f t e r d e t e r m i n at i o n o f t h e d i m e n s i o n s o f t h e c r o s s - s e c t i o n t h e y werel o a d e d i n a t e s t i n g m a c h i n e w i t h t h e l o a d a n d e l o n g at i o n r e c o r d e d on a c h a r t . With t h e e x c e p t i o n o f t h es p e c i m e n s u s e d f o r d e t e r m i n i n g t e n s i l e m o d u l u s , t h e

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7/9

3 , 9 5 7 , 7 2 77e l o n g a t i o n c o r r e s p o n d i n g t o r e l a t i v e g r i p movementwas recorded. An extensometer or s t r a i n gauge wasmounted on t h e specimen t o measure e l o n g a t i o n whend e t e r m i n i n g modulus v a l u e s . T e n s i l e modulus o f e l a st i c i t y was d e t e r m i n e d from t h e i n i t i a l s l o p e o f t h e l o a ds t r a i n curve. All t e s t s were carried o u t at room temperature.The e l o n g a t i o n a n d d u c t i l i t y i s m a i n t a i n e d o v e r a

w i d e r a n g e o f c o n c e n t r a t i o n s o f a c i d a n d a n h y d r i d ew i t h t h e t e n s i l e s t r e n g t h s v a r y i n g b e t w e e n 1 5 3 0 0 t o17300 l b / i n 2 a s shown i n Table .

1 0

TABLE

8a . A u r a b l e c o m p o s i t i o n w a s p r e p a r e d c o n s i s t i n g o f

1 0 0 p a r t s b y w e i g h t o f a DEN 3 1 n o v o l a c r e s i n , 6 0p a r t s b y w e i g h t o f NMA c i d - a n h y d r i d e c o m p o u n dh a v i n g a r a t i o o f a n h y d r i d e z a c i d o f a b o u t 5 : 1 and 3 0p a r t s b y w e i g h t o f p h t h a l i c a n h y d r i d e w i t h 0 . 1 5 %BDMA a t a l y s t .

T h i s c o m p o s i t i o n was used t o p r e p a r e t e s t s a m p l e su s i n g t h e p r o c e d u r e o f E x a m p l e 2 . T h e s e s a m p l e s w e r et h e n c u r e d under a v a r i e t y o f c o n d i t i o n s and t h e s t r e s sand e l o n g a t i o n o f t h e s e c u r e d s a m p l e s was d e t e r m i n e d .The r e s u l t s a r e shown i n Table 2 b e l o w .

T NSlL RESULTS FROM A SERIES OFAClD-ANHYDRIDE COMPOUND AND PHTHALlC ANHYDRIDE COMBlNATlONS

AClD-ANHYDRIDE COMPOUND, PHR1 5 25 35 40 47 60 80 90 100 1 0 5

PHTHALlC 0 15270 15570 15400 15330ANHY- 5DRlDE,PHR 1 O

1 5 1 6 1 1 020 159602 5 16090 1550030 1620035 1620040 16510 CATALYSlS CONCENTRATION:45 16580 15920 0 . 2 5 PARTS PER HUNDRED OF50 16250 15550 AClD-ANHYDRIDE COMPOUNDCURE: 100C FOR HR.55 16850 16750 160C FOR HR.60 17020 16950 16840 ELONGATION: 8 9%6 5 16660 16240 MODULUS: . 4 0 . 5 > < 1 0 B LB/lN270 17260 AN/A OFCOMPOUND: . 975 EPOXY NOVOLAC RESIN DEN 431

TABLE 2Max E 1 o n g *P r e c u r e P o s t Cure S t r e s s ( a t b r e a k )Temp. C Time H r . Temp. C Time h r . p s i

1 . 100 6 160 8 16200 92 . 100 6 160 1 6 16513 9 . 13 . 80 24 I60 8 16599 9 . 34 . 100 6 160 8{ o ? o v e m i t e p l u s }100 6 160 8 16375 9 . 55 . 6O 24 160 6 15940 8 . 26 . 100 6 160 50 min.{ o f f 2 % r s . + 1 6 0 1 h r . 1 0 m i n . }o f f ovemite + 160 5 h r s . 16427 9 . 27 . 100 6 160 2 16211 9 . 2 N o t e :The s t r a i n was e s t i m a t e d from t h e e x t e n s i o n between g r i p s .

Example 3 b . Followmg t h e same g e n e r a l p r o c e d u r e a s ( a )50A e r i e s of t e s t s were conducted w i t h d i f f e r e n t cura b l e c o m p o s i t i o n s o f t h e i n v e n t i o n and t h e s e were

c u r e d u n d e r a v a r i e t y o f c o n d i t i o n s which d e v i a t e df r o m t h e o p t i m u m .

a b o v e , s a m p l e s w e r e p r e p a r e d , c u r e d and t e s t e d u s i n g ac u r a b l e c o m p o s i t i o n c o n s i s t i n g o f 1 0 0 p a r t s b y w e i g h to f a DEN 3 1 n o v o l a c r e s i n and 9 5 p a r t s b e w e i g h t o fNMA c i d - a n h y d r i d e compound h a v i n g a r a t i o o f a nh y d r i d e z a c i d o f 5 : 1 w i t h 0.24% BDMA a t a l y s t . Ther e s u l t s a r e shown i n Table 3 b e l o w .

TABLEMax E l o n g . P r e c u r e P o s t Cure S t r e s s ( a t b r e a k )Temp. C Time H r . Temp. C Time H r . p s i

1 . 100 6 160 8 15529 92 . 100 6 160 1 6 15763 8 . 63 . 80 24 160 8 15471 8 . 84 . 100 6 160 8{ o f f o v e r n i t e p l u s }100 6 160 8 15626 9 . 55 . 60 24 160 6 15477 8 . 26 . 100 6 160 2 14524 6 . 4 * *7 . 100 6 160 4 15564 8 . 98 . 100 6 180 8 15081 7 . 3 * *9 . 100 6 200 8 15593 8 . 3B r i t t l e f r a c t u r e

1 N o t e :The s t r a i n was e s t i m a t e d f r o m t h e e x t e n s i o n between g r i p s .

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90 . F o l l o w i n g t h e same g e n e r a l p r o c e d u r e a s ( a )

a b o v e , s a m p l e s w e r e p r e p a r e d , c u r e d a n d t e s t e d u s i n g ac u r a b l e c o m p o s i t i o n c o n s i s t i n g o f 1 0 0 p a r t s b y w e i g h to f a DEN 4 3 1 n o v o l a c r e s i n , 8 0 p a r t s b y w e i g h t o fNMA c i d - a n h y d r i d e compound h a v i n g a r a t i o o f a nh y d r i d e z a c i d o f 5 : 1 , 1 5 p a r t s b y w e i g h t o f p h t h a l i c a nh y d r i d e and 0.20% BDMA a t a l y s t . The r e s u l t s a r eshown i n Table 4 b e l o w :

3 , 9 5 7 , 7 2 7

5

1 0a c i d - a n h y d r i d e compound o f t h e i n v e n t i o n h a v i n g ar a t i o o f a n h y d r i d e z a c i d o f a b o u t 5 : 1 , p h t h a l i c a n h y d r i d e(PA) and a m i x t u r e o f t h e NMA c i d - a n h y d r i d e comp o u n d a n d p h t h a l i c a n h y d r i d e . T h e c a t a l y s t s i n c l u d e dt e r t i a r y a m i n e s a v a i l a b l e f r o m Rohn a n d Haas u n d e rt h e trademarks DMPlO, and DMP 30, a CIBA c a t a l y s th a v i n g t h e d e s i g n a t i o n 0 6 5 a n d a n a m i d e c a t a l y s t d ev e l o p e d b y N a t i o n a l A e r o n a u t i c a l E s t a b l i s h m e n t , O t

TABLE, Maximum Elong.*

P r e c u r e P o s t Cure S t r e s s ( a t b r e a k )Temp. C Time H r . Temp. C Time - I r . p s i1 . I00 6 I60 8 15938 92. I00 6 I80 8 16017 8 . 93 . 100 6 200 8 16033 8

N o t e :The s t r a i n was e s t i m a t e d from t h e e x t e n s i o n between g r i p s .

E x a m p l e 4An NMA c i d - a n h y d r i d e c o m p o u n d w a s p r e p a r e d f o l l o w i n g t h e p r o c e d u r e o f E x a m p l e 1 ( b ) t o p r o v i d e acompound w i t h a n a n h y d r i d e ' z a c i d l r a t i o o f 3 . 7 : 1 . With

2 0 t a w a , shown u n d e r t h e d e s i g n a t i o n N o . 1 c a t a l y s t . Thep r o p o r t i o n s o f c o m p o n e n t s , c u r i n g c o n d i t i o n s a n ds t r e n g t h t e s t r e s u l t s a r e a l l s e t o u t i n Table 5 .

E x a m p l e 61 0 0 p a r t s o f DEN 3 1 n o v o l a c r e s i n w e r e m i x e d 6O 2 5 A e r i e s o f t e s t s a m p l e s were p r e p a r e d f r o m ERL

TABLESample C r o s s - L i n k i n g Agent C a t a l y s t F i r s t Cure Second Cure Ma x l o n g RemarksNo Type Conc. Type Cone. Temp. Time Temp. Time S t r e s s ( a t b r e a k )

p h r j ' p h r C. h r . C. h r . p s i1 NMA 9 0 No . 1 ' 2 120 3 1 ' 5 0 4 1 1 7 72 4.5 B r i t t l e2 NMA 90 No. l 2 . 1 0 0 6 160 8 l 1290 6 Y i e l d3 NMA 90 No. l 4 I00 6 I60 8 1 5 030 8 B r i t t l e

4 NMA 90 No. l 5 . 3 1 2 0 3 I50 8 l 1547 4 . 5 B r i t t l e5 NMA 90 No. 4 120 3 150 8 1 4 8 3 8 8 ' Ductile6 NMA 90 065 0.83 120 3 150 8 1899 100 Co l d F l ow7 Acid-Anhyd. 80 No. l 2 120 2 1 5 0 4 14006 8 . 5 D u c t i l e8 Acid-Anhyd. 80 No. l 2 100 6 160 8 13859 8 . 5 D u c t i l e9 Acid-Anhyd 80 No. l 4 120 3 150 8 13415 8 D u c t i l e1 0 PA 75 No. l 0 . 6 7 120 3 150 4 15119 9 D u c t i l el l PA 75 No. l 1 . 3 4 120 3 I50 8 15367 9 Ductile12 Acid-Anh.+PA 60 + 0 DMPIO 0.25 100 6 160 8 15166 6 . 7 B r i t t l el 3 Acid-Anh.+PA 60 + 20 No. l 2 120 3 I50 4 I 5 33 7 . 5 D u c t i l e14 Acid-Anh.+PA 60 + 20 DMP30 0 . 2 5 100 6 160 8 14946 8 D u c t i l e15 Ac id- A nh . + P A 60 +20 No. 1 2 120 3 150 8 15091 6 . 5 B r i t t l el6 Acid-Anh.+PA 60 + 0 065 0.83 120 3 150 8 13710 6 B r i t t l e

_ NOTE: A c i d - A n h y d . i s NMA c i d a n h y d r i d e compound o f i n v e n t i o n h a v i n g a r a t i o o f a n h y d r i d e z a c i d o f a b o u t 5 : 1.DMPlO s a trademark of Rohm & Haas f o r a t e r t i a r y - a m i n e c a t a l y s tDMP30 s a trademark o f Rohm & Haas f o r a t e r t i a r y - a m i n e c a t a l y s t065 i s a t r a d e d e s i g n a t i o n f o r a CIBA a t a l y s tN o . l i s a h o u s e d e s i g n a t i o n f o r a n a m i d e c a t a l y s t d e v e l o p e d b y N a t i o n a l A e r o n a u t i c a l E s t a b l i s h m e n t , O t t a w a , Canada

c a t a l y s t . T h i s m i x t u r e was h e a t e d w i t h s t i r r i n g t o a b o u t1 0 0 C t o o b t a i n a c l e a r y e l l o w i s h l i q u i d c u r a b l e r e s i n mix.

T h i s c u r a b l e r e s i n was t h e n u s e d i n i n s u l a t i n g compon e n t s o f a s p e c i a l 2 0 , 0 0 0 v o l t s w i t c h . The c o m p o n e n t swere wrapped i n g l a s s c l o t h , assembled i n a mold andi m p r e g n a t e d w i t h t h e a b o v e l i q u i d r e s i n m i x . The e s i nm i x , t h e s w i t c h components and t h e mold w e r e h e a t e ds e p a r a t e l y t o a b o u t 1 0 0 C b e f o r e a d d i n g t h e r e s i n t ot h e m o l d . A f t e r t h e r e s i n was a d d e d , t h e s ys t e m wase v a c u a t e d and t h e n t h e mold was p r e s s u r i z e d t o 50 p s i gi n a h e a t e d p r e s s and c u r e d f o r 6 h r . a t 100C and 8 h r .a t 1 6 0 C .

E x a m p l e 5A e r i e s o f t e s t s a m p l e s were p r e p a r e d from EPON

8 2 8 e p o x y r e s i n w i t h d i f f e r e n t c r o s s - l i n k i n g a g e n t s a n dc a t a l y s t s . F o u r d i f f e r e n t c r o s s - l i n k i n g a g e n t s w e r e u s e d ,i n c l u d i n g n a d i c m e t h y l a n h y d r i d e (NMA), t h e NMA

60

65

. p a r t s o f t h e a b o v e a c i d - a n h y d r i d e c o m p o u n d , 3 0 p a r t s 5 0 4 2 8 9 e p o x y r e s i n w i t h d i f f e r e n t c r o s s - l i n k i n g a g e n t sp h t h a l i c a n h y d r i d e a n d 0 . 1 % b e n z y l d i m e t h y l a m i n e a s and c a t a l y s t s , t h e s e b e i n g t h e same a s i n Example 5 .T h e p r o p o r t i o n s o f c o m p o n e n t s , c u r i n g c o n d i t i o n s a n ds t r e n g t h t e s t r e s u l t s a r e a l l s e t o u t i n Table 6 .

5 5E x a m p l e 7

I n o r d e r t o i l l u s t r a t e t h e d u c t i l i t y o f t h e r e s i n o f t h ei n v e n t i o n , s t r e s s - s t r a i n d a t a was o b t a i n e d on a sampleo f t h e r e s i n o f t h e i n v e n t i o n a s w e l l a s on t h r e e t y p i c a lcommercial e p o x y s y s t e m s . T h i s d a t a was p l o t t e d t oform t h e c u r v e s o f F I G . 2 .Curve 1 i s f o r ERLA 4617 epoxy r e s i n w i t h metap h e n y l e n e d i a m i n e , w h i l e c u r v e 2 i s f o r DEN 438e p o x y r e s i n w i t h NMA r o s s - l i n k i n g a g e n t a n d BDMAc a t a l y s t . Curve 3 i s f o r ERLA 2772 e p o x y r e s i n w i t hZZL 0822 c r o s s - l i n k i n g a g e n t . F i n a l l y , c u r v e 4 i s f o rr e s i n s o f t h e i n v e n t i o n , i . e . DEN 3 1 c r o s s - l i n k e d w i t ht h e NMA c i d - a n h y d r i d e c o m p o u n d .

C u r v e s l a n d 2 a r e t y p i c a l e x a m p l e s o f b r i t t l e f r a ct u r e w h i l e c u r v e s 3 and 4 i l l u s t r a t e d u c t i l i t y .

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3 , 9 5 7 , 7 2 7' 1 1 12TABLE 6

S a m p l e C r o s s - L i n k i n g A g e n t C a t a l y s t F i r s t C u r e S e c o n d C u r e Max l o n g . RemarksNo Type C o n c . Type C o n c . Temp. Time Temp. Time S t r e s s ( a t b r e a k )p h r p h r C . h r . C . h r . p s iA NMA 80 No. l 2 I00 6 I60 8 7 Solid ?e x i ble weakB NMA 80 No. l 4 I00 6 I60 8 Solid ?exibles t r o n g e rC NMA 80 DMPlO l 100 6 I60 8 1904 40- 4 5 D NMA 80 065 0.83 100 6 I60 8 10102 8 . 9 D u c t i l eE NMA 8 0 BDMA 0.83 100 6 I60 8 ~ So? ?exible weakF Acid-Anhyd. 68 No. l 2 I 2 0 3 I 5 0 4 6886 20 D u c t i l eG Acid-Anhyd. 68 No. l 2 I20 3 I50 8 9050 1 5 D u c t i l eH Acid-Anhyd. 68 No. l 2 1 0 0 6 I60 8 9550 9 D u c t i l e

l Acid-Anhyd. 68 DMPlO 0 . 2 5 I00 6 160 8 l0l58 6 . 7 B r i t t l e. l Acid-Anhyd. 68 DMP30 0 . 2 5 I00 6 I60 8 l 0 3 l 9 8 D u c t i l eK Acid-Anhyd. 68 0 6 5 0 . 8 3 l20 3 I50 8 l l 180 8 D u c t i l eL Acid~Anhyd. 68 BM? O 0 . 5 120 3 I50 8 l 0496 7 B r i t t l eNOTE:Acid-Anhyd s NMA c i d - a n h y d r i d e compound o f i n v e n t i o n h a v i n g a r a t i o o f a n h y d r i d e z a ci d o f a b o u t 5 : lDMPIO s a trademark o f Rohm & Haas f o r a t e r t i a r y a mine c a t a l y s tDMP30 s a trademark o f Rohm & Haas f o r a t e r t i a r y a mine c a t a l y s t065 i s a t r a d e d e s i g n a t i o n f o r a ClBA c a t a l y s tNo. l i s a h o u s e d e s i g n a t i o n f o r a n amide c a t a l y s t d e v e l o p e d b y N a t i o n al A e r o n a u t i c a l E s t a b l i s h m en t . O t t a w a , C a n a d a .

We l a i m :1 . A e a t c u r a b l e c o m p o s i t i o n o f m a t t e r c o m p r i s i n g( 1 ) a n epoxy r e s i n s e l e c t e d from t h e group c o n s i s t i n go f d i g l y c i d y l e t h e r o f b i s - p h e n o l A , e p o x i d i z e d n o v o l a cr e s i n s and c y c l i c a l i p h a t i c e p o x y r e s i n s and ( 2 ) a s c u ri n g a g e n t a n a c i d - a n h y d r i d e compound h a v i n g a n a n h yd r i d e to a c i d r a t i o i n t h e r a n g e o f from 3 - 1 2 1 1 o b t a i n e db y h e a t i n g m e t h y l e n d o m e t h y l e n e t e t r a h y d r o p h t h a l i ca n h y d r i d e w i t h t h e s t o i c h i o m e t r i c a m o u n t o f w a t e rr e q u i r e d t o p r o d u c e t h e r e q u i r e d a n h y d r i d e - a c i d r a t i o .2 . A o m p o s i t i o n a c c o r d i n g t o c l a i m 1 w h e r e i n a b o u t5 0 t o 1 5 0 p a r t s b y w e i g h t o f c r o s s - l i n k i n g a g e n t a r ep r e s e n t p e r h u n d r e d p a r t s b y w e i g h t r e s i n .3 . A o m p o s i t i o n a c c o r d i n g t o c l a i m 2 w h e r e i n t h er a t i o o f s a i d anhydride t o s a i d a c i d i s 3 1 0 : 1 .

4 . A o m p o s i t i o n a c c o r d i n g t o c l a i m 2 w h e r e i n ana d d i t i o n a l a n h y d r i d e c r o s s - l i n k i n g a g e n t i s p r e s e n t , t h e

25

35

40

45

50

55

60

65

t o t a l amount o f c r o s s - l i n k i n g a g e n t b e i n g a b o u t 5 0 t o1 5 0 phr.5 . A o m p o s i t i o n a c co r d i n g t o c l a i m 4 w h e r e i n t h ea d d i t i o n a l a n h y d r i d e i s s e l e c t e d f r o m t h e g r o u p c o n s i s ti n g o f p h t h a l i c a n h y d r i d e , t e t r a h y d r o p h t h a l i c a n h yd r i d e , h e x a h y d r o p h t h a l i c a n h y d r i d e , s u c c i n i c a n h yd r i d e a n d d o d e c e n y l s u c c i n i c a n h y d r i d e .6 . A o m p o s i t i o n a c c o r d i n g t o c l a i m 4 w h e r e i n up t o7 0 p h r o f t h e a d d i t i o n a l a n h y d r i d e i s p r e s e n t .7 ; A o m p o s i t i o n a c co r d i n g t o c l a i m 2 w h e r e i n t h ee p o x y component s a n o v o l a c r e s i n h a v i n g a n e q u i v al e n t w e i g h t o f a b o u t 1 7 5 .8 . A o m p o s i t i o n a c co r d i n g t o c l a i m 7 w h e r e i n t h ea m o u n t o f c r o s s - l i n k i n g a g e n t i s a b o u t 8 0 t o 1 0 5 p h r .9 . A o m p o s i t i o n a c co r d i n g t o c l a i m 8 w h e r e i n t h eamount o f c r o s s - l i n k i n g a g e n t i s a b o u t 90 t o 9 5 p h r .

* * > | = * * -