用附着型促进剂制备橡胶蒙脱土纳米复合材料.pdf

第 2 l卷第 6期 Vo 1 2 l N o 6 2 0 0 6年 1 1 月 NO V 2 0 0 6 热 固 性 树 脂 T h e r mo s e t t i n gRe s i n 1 Y of n a t u r a l r u b b e r mo n t mo r i l l o n i t e a d h e s i v e a c c e l e r a t o r P】B s OU Ya n gx i n g，LUO Yu a n gf a n g，J I A Demi n，F U We i we n，L I U L a n (C o l l e g e o f Ma t e r i a l S c i e n c e a n d E n g i n e e r i n g，S o u t h C h i n a Un i v e r s i t y T e c h n o l o g y，G u a n g z h o u 5 1 0 6 4 0，C h i n a)Ab s t r a c t：Th e n a t u r a l r u b b e r mo n t mo r i l l o n i t e n a n o c o mp o s i t e s we r e p r e p a r e d wi t h a d h e s i v e a c c e l e r a -t o r P BS b y mi x i n g i n t e r c a l a t i o n me t h o d B e c a u s e mo s t o f t h e a c c e l e r a t o r r a d i c a l g r o u p wa s l i n k e d o n t h e r u b b e r c h a i n s a f t e r c u r i n g，u s i n g t h e a c c e l e r a t o r wh o s e r a d i c a l g r o u p S e n d c o u l d i n t e r a c t wi t h t h e mo n t mo r i l l o n i t e l a y e r s，t h e i n t e r a c t i o n b e t we e n mo n t mo r i l l o n i t e f l e e t s a n d r u b b e r c h a i n s c o u l d b e e n h a n c e d，a n d n a t u r a l r u b b e r mo n t mo r i l l o n i t e n a n o c o mp o s i t e s wi t h g o o d c o mp r e h e n s i v e p r o p e r t i e s c o u l d b e p r e p a r e d 0n t h e e f f e c t o f t h e a d h e s i v e a c c e l e r a t o r P B Si t c o u l d d e c r e a s e a c t i v a t i o n e n e r g y o f c u r i n g a n d t h e n e w s y s t e m w i t h t h e o r g a n i c mo n t mo r i l l o n i t e(HMT)h a d l a r g e r c r o s s l i n k i n g d e n s i t y An d t h e n a t u r a l r u b b e r mo n t mo r i l l o n i t e n a n o c o mp o s i t e s h a d g o o d me c h a n i c a l p r o p e r t i e s Wh e n a d d i n g 8 HM T，1 0 0 mo d u l u s i n c r e a s e d f r o H I 1 2 0 MP a t o 2 2 0 MP a 5 0 0 mo d u l u s i n c r e a s e d f r o I n 8 1 2 MP a t o 1 8 2 3 MP a S h o r e A h a r d n e s s e n h a n c e d f r o m 4 5 t o 5 5 Wh e n j u s t a d d 2 p h r HMT i t c a me o u t a b i g v a l u e，5 0 0 mo d u l u s r a n g e s f r o m 8 1 2 MP a t o 1 7 0 6 MP a a n d t e a r s t r e n t h r a n g e s f r o m 3 6 3 1 k N m t o 4 3。6 5 k N m，i n o t h e r wo r d s，8 p h r HMT wa s c o mp a r a b l e t o 4 0 p h r s e mi r e i n f o r c e d c a r b o n Th e me c h a n i c a l p r o p e r t i e s o f NR wi t h 2 1 0 p h r HM T wa s c o mp a r a b l e t o t h e C O H I-p o u n d wi t h 4 0 p h r s e mi r e i n f o r c e d c a r b o n b l a c k Ke y wo r d：a d h e s i v e a c c e l e r a t o r；n a t u r a l r u b b e r；HMT：n a n o c o mp o s i t e s 用附着型促进剂制备橡胶 蒙脱土纳米复合材料 欧阳星，罗远芳，贾德民，傅伟文，刘 岚(华南理工大学材料学院，广东广州 5 1 0 6 4 0)摘要：用附着型促进剂 P B S 在机械混炼插层法的基础上制备了天然橡胶 蒙脱土纳米复合材料。由于硫化后大 部分促进剂基团都连在橡胶分子链上，因此用分子一端能和蒙脱土片层有相互作用的附着型硫化促进剂，可以 大大增强蒙脱土和橡胶基体的相互作用，得到性能优 良纳米复合材料。用 P B S制备纳米复台材料其硫化体系活 性能低，硫化胶交联密度增大，有机蒙脱土片层在橡胶基体中达到纳米级的分散，具有优良的力学性能，加入 8 有机蒙脱土 1 0 0 模量从 1 2 MP a 增至 2 2 M P a，5 0 0 模量从 8 1 2 M P a 增至 l 8 2 3 M P a，邵氏 G A硬度从 4 5增至 5 5，而加入 2 有机蒙脱土 5 0 0 模量从 8 1 2 MP a 增至 1 7 0 6 MP a，撕裂强度从3 6 3 1 k N m增至4 3 6 5 k N m，加入 2 1 0 份有机蒙脱土时其效果相当于加入 4 O份半补强炭黑。关键词：附着型促进剂；天然橡胶；有机蒙脱土；纳米复合材料 中国分类号：T B 3 8 3 文献标识码：A 文章编号：1 0 0 27 4 3 2(2 0 0 6)0 60 0 0 1 0 5 【收稿日期】2 0 0 6 0 2 1 5 【基金项目】国家自 然科学基金资助项目(5 0 5 7 3 0 2 1)(作者简介】欧阳星(1 9 8 0 )，男，博士生，研究方向为有机 无 机纳米复合材料。0 l n t r o d u c t i o n Na t u r a l r u b b e r mo n t mo r i l l o n i t e n a n o c o mp o s i t e s b e c o me mo r e a n d mo r e p o p u l a r f o r t h e i r e x c e l l e n t p e r-f o r ma n c e b y a d d i n g a f e w a mo u n t o f mo n t mo r i l l o n i t e，a n d t h e p e r f o r ma n c e o f t h e r u b b e r mo n t mo r i l l o n i t e 维普资讯 http:/ 热 固 性 树 脂 第 2 l 卷 na n o c o mpo s i t e s f r o m t wo r e s p e c t s wa s g e n e r a l l y i m p r o v e dOn e wa s ma k i n g mo n t mo r i l i o n i t e l a y e r s r e a c h t h e g o o d d i s p e r s i o n i n t h e r u b b e r ma t r i x a t f i r s t S o v a r i o u s wa ys we r e a d o p t e d t o g e t i t，s u c h a s i n s i t u i nt e r c ala t i v e p o l y me r i z a t i o n，e x f o l i a t i o na d s o r p t i o n，mi x i n g i n t e r c 8 l a t i o n me t h o d -7 1 a n d s o o n S i n c e mi x i ng i nt e r c a l a t e me t ho d wa s e c o n o mi c a l，e n v i r o n me nt all y s a f e a nd p r a c t i c al，t hu s i t a t t r a c t e d mo r e a n d mo I|e a t t e n t i o ns bv r e s e a r c he r s l 8 t t 1L i u【。u s e d mi x i n g i nt e r c ala t i o n me t h o d t o p r e p a r e f o r NBR mo n t mo r i l l o n i t e n a n o c o mp o s i t e s，i t s p r o p e r t i e s we r e C O B p a r a b l e wi t h 3 0 p h r N3 3 0 fi l l e d r u b b e r t o s o me d e g r e eZh e n g l l o h a d ma d e t he r e s e a r c h o n t h e i n flu e n c e b y u s i n g d i f f e r e n t v u l c a n i z a t i o n s y s t e ms t o p r e p a r e f o r EPDM mo nt mo r i l l o n i t e na no c o mp o s i t e s，a nd u s i n g EPD M g r a f t e d ma l e i c a n hy d r i d e a s i t s c o mp a t i l-i z e r t o g e t e x f o l i a t e d EPDM mo nt mo r i llo n i t e n a n o c o mp o s i t e s wi t h e x c e ll e n t me c h a n i c a l p r o p e r t i e s T h e o t he r w as t ha t s t r e n g t h e n t h e i n t e r a c t i o n b e t we e n mo n t mo r i l i o n i t e fl e e t s a n d r u b b e r ma t r i x c o ald i m p r o v e i t s c o mp r e h e n s i v e p r o p e r t i e s J i a I h a d e n h a n c e d t h e i nt e r a c t i o n b e t we e n o r g a n i c mo n t mo r i U o n i t e fl e e t s a n d r u b ber c h a i n s b y a d d i n g t h e t h i r d mo n ome r d ur i ng t h e mi x i n g p r o c e s s t o g e t r u b b e r mo nt mo r i I I on i t e na n o c o mp o s i t e s wi t h e x c e ll e nt p e r-f o r ma n c e W a n g 1 3 _ ma d e o r g a n i c mo n t mo r i l l o ni t e p r e p a r e d b y s o l i d s t a t e me t h o d wi t h r e a c t i v e mo n o me r a t fi r s t，a n d j o i n mo n t mo r i l l o n i t e fl e e t s a n d r u b b e r c h a i n s t h r o ug h t he c h e mi c al r e a c t i o n b y t h e p r o c e s s i n g o f mi x i n g i n t e r c a l a t i o n a n d c u r i n g t o a c h i e v e r u b b e r mo n t mo r i l l o ni t e n a n o c o mp o s i t e s Ho we v e r，all t he c u r r e n t v u l c a ni z a t i on s y s t e ms t o p r e p a re f o r na t u r al r u b b e r mo nt mo rill o ni t e na n o-c o mp o s i t e s we r e u s i n g t h e n o r mal v u l c a n i z a t i o n a c c e l-e r a t o r T h e n o r ma l v u l c a n i z a t i o n a c c e l e r a t o r c o u l d n o t b r i n g t h e l a y e r s o f mo n t mo r i l i o n i t e i n t o r u b b e r c h a i n s d u r i n g t h e v u l c a n i z a t i o n p r o c e s s I n t h i s a r t i c l e，i n t e r ms o f a c c e l e r a t o r t o e n h a n c e t he i n t e r a c t i o n b e t we e n mo nt mo r i llo n i t e a nd r u b b e r c h a i ns we r e c o n s i d e r e d Ac c e l e r a t o r a r e ac t i v e mo l e c u l e i n t h e c u r i n g s y s t e mAf t e r c u r i n g mo s t o f t h e a c c e l e r a t o r r a d i c al g r o u p j o i n e d o n t h e r u b b e r c h a i n s，s o i f o n e o f r a d i c a l gr o u p s e n d c o u l d i nt e r a c t wi t h t h e mo n t mo r i l l o n i t e l a y e r s，mo nt mo r i l l o n i t e fle e t s wo u l d be br o u g ht i n t o t h e r u b b e r n e t wo r k i n t h e p r o c e s s o f c u ri n g Th e r e for e，t h e i n t e r a c t i o n b e t we e n mo n t mo r i U o n i t e fl e e t s a n d r u b b e r c h a i n s wa s e n h a n c e d，a n d t h e c o mp r e-h e n s i v e p r o p e r t i e s o f n a n o c o mp o s i t e s wa s i mp r o v e d He r e a n e w v u l c a n i z a t i o n a c c e l e r a t o r c a l l e d a d h e s i v e a c c e l e r a t o r P BS wa s i n t r o d u c e d t o p r e p a r e n a t u r al r u b be r mo n t mo r i l i o n i t e n a n o c o mpo s i t e s Th e s c h e ma t i c s t r u c t u r e o f Ad h e s i v e Ac c e l e r a t o r P BS c o u l d b e e x p r e s s e d b y t h e f o l i o wi n g：一 cooH F i g 1 T h e s c h e ma t ic s t r u c t u r e o f a d h e s iv e a c c e l e r a t o r P BS Be n z o t h i a z o l e s u l f e n a mi d e o n t h e l e f t o f t h e s c h e ma t i c i n f i g 1 wa s a e f f i c i e n t c u r i n g a c c e l e r a t o r g r o u p，p r o p y l be t a i n e o n t h e r i g h t o f t h e s c h e ma t i c h a d hy d r o g e n b o n ds o n t he s ur f a c e o f t he mo n t mo r i l l o n i t e fl e e t s b y h y d r o x y l g r o u p Th e r e f o r e P BS c a n l i n k mo n t m o r i l i o ni t e fle e t s t o r u b be r c ha i ns，i eTh e r e wo u l d b e s t r o n g h y d r o g e n b o n d s t r e n g t h wi t h mo n t mo r i l l o n i t e fl e e t s a n d r u b be r c h a i n s，t h u s t h e e x i s t e n c e o f a d h e s i v e s t r e n g t h wo u l d b r i n g mo n t mo r i l l o n i t e fle e t s i n t o t h e r u b b e r n e t wo r k i n t h e p r o c e s s o f c u r l n gTh e r e f o r e，i t e n h a n c e d t h e i n t e r a c t i o n b e t ween mo n t mo r i l i o n i t e fl e e t s a n d r u b be r c h a i n s，i mp r o v i n g i t s c o mp r e h e n s i v e p r o per t i e s，wh i l e t h e a c t i v i t y o f a d h e s i v e a c c e l e r a t o r h a d a l s o b e e n i mp r o v e d b y H M T I n t hi s a r t i c l e，t h e na t u r al r u b b e r mo nt mo r i l l o n i t e n a n o c o mp o s i t e s we r e p r e p a r e d by i n t r o d u c i ng t h i s k i n d o f a c c e l e r a t o r P B S a n d t h e c u r i n g be h a v i o r，t h e s t r u c t ur e a n d me c ha n i c a l pr o p e r t i e s we r e s t u d i e d 1 E x p e r i me n t a l 1 1 Ma t e r i a l s N a t u r a l r u b ber(N R)o f S MRL g r a d e w a s p u r c h a s e d f r o m Gu t h r i e C o r p B h d Ma l a y s i a；O r g a n i c mo n t mo r i l-l o n i t e(HMT)w a s p r e p a r e d b y a c a t i o n i c e x c h a n g e p mo e 够 i n a l l a q u e o u s s o l u t i o n b y v i g o r o u s l y s t i r ri n g sod i u m mo n t mo r i l l o n i t e wh i c h was dis p e r s e d i n dis t i l l e d wa t e r wi t h h e x a d e c y l t r i me t h y l a mmo n i u m b romi d e；Ad h e s i v e a c c e l-e r a t o r(P B S)：t h e s y n t h esi s o f P B S w as t h rou g h o x i di z a t i o n b y 2 me r e a p t o ben z o t h i a z o l e a n d a mi n o p r o p y l b e t a i n e b y mP A t n$o f h y d rog e n p e rox i d e a s o x i d a n t，ma d e b y t h e g rou pi t s e l f；a c c e l e r a t o r C Z：N c y c l o h e x y l 2 ben z o t h -i a z o l e s u l f e n a mi d e s u p p l i e d Z h u Z h o u T i an C h e n c h e mi-维普资讯 http:/ 第 6期 欧阳星等：用附着型促进剂制备橡胶 蒙脱土纳米复合材料(英文)3 c a l c o m p a n y；C a r b o n b l a c k(C B)：s u p p l i e d b y C h o n g Q i n Wo l o n g c h e mi c a l C o mp a n y；A l l t h e l e f t we re t h e c o mmo n r u b b e r a c c e s s o r y i n g r e d i e n t，c h e mi c a l l y p u r e t i o n f o r na t u r al l u b be r mo nt mo r i 1 1 o-n i t e na n o c o mpo s i t e s Th e r u b b e r c o mp o n e n t s we r e mi x e d o n a t wo*r o l l l a b o r a t o r v mi l l o f o u t s i d e d i a me t e r 1 6 O mmTh e o r d e r f o r a d d i n g t h e ma t e r i al：N R a c t i v a t o r(Z n O，S t e a r i c a c i d)一 r e i n f o r c i n g f i l l e r(HMT o r CB)一 a c c e l e r a t o r s u l f u r Th e c o mp o u n d wa s c u r e d i n p r e s s a t 1 4 3 t h e n wo u l d b e t e s t e d o v e r n i g h t T h e r e c i p e s w a s NR 1 0 0 p h r，a c t i v a t o r(Z n O 5 p h r，S t e a r i c a c i d 2 p h r)，r e i n f o r c i n g f i l l e r(H M T v a r i a b l e o r C B 4 0 p h r)，c u r i n g a g e n t(C Z 2 p h r，S 1 5 p h r o r P B S 4 p h r，S 3 p h r)1 3 Cha r a c t e r i z a t i o n s a nd t e s t i ng Th e c u ri n g b e h a v i o r o f t h e c o mp o u n d s w a s d e t e r-m i n e d u s i n g a l l o s c i l l a t i n g d i s k r h e o m e t e r(U N 2 0 3 0，C h i n a)a c c o r d i n g t o G B 9 8 6 9-1 9 8 8 A c c o r din g t o A r r h e n i u s f o r mu l a，wh e re K i s c u ri n g r a t e c o n s t a n t；A i s c o n s t an t；i s act i v a t i o n e n e r g y o f c u rin g；R i s g as c o n s t an t；T i s c u rin g t e mp e r a t ur e Us i n g t=T9 0 一 T1 0 t o e x-p r e s s t h e r a t e c o n s t an t K，g e tUs i n g 1 T a s t h e v a ri a b l e f o r I n(t)t o d r a w t h e g r a p h。g e t t i n g t h e act i v a t i o n e n e r g y o f c u rin g b y t h e s l o p e o f t h e h n e。Xr a y d i ff r a c t i o n(XRD)wa s c a r r i ed o u t u s i n g a d i f f r act o m e t e r(D ma x I l i A，J a p a n)u s i n g C u k口r a d i-a t i o n a t a g e n e r a t o r v o l t a g e o f 4 0 k V and a g e n e r a t o r c u r-r e nt o f 1 0 0 mATh e d i f f r act o g r a m was s c a n ned i n t h e 2 0 r a n g e f r o m 1 o t o 4 5。a t a r a t e o f 2 mi n Cr o s s l i n k i n g d e n s i t y wa s d e t e r mi n e d b y e q u i l i b-r i um s we l l i n g S a mp l e s we r e s wo l l e n i n h e x a n e a t r o o m t e mp e r a t u r e t o e q u i l i b r i u m，a n d t h e n r e mo v e d f r o m t h e s o l v e n t a n d t h e s u r f a c e h e x a n e wa s q u i c k l y b l o t t e d o f f wi t h t i s s u e p a p e r Th e s a mp l e s we r e i m me d i a t e l y we i g h t e d o n a n a n a l y t i c a l b a l a n c e t o t h e t o l-e r a n c e o f 1 mg a n d t h e n v a c u u m d r i e dAs s u mi n g t h e ma s s l o s s o f t h e r u b b e r d u r i n g s we ll i n g i s t h e s a me f o r a l l t h e s a mp l e s，t h e v o l u me f r a c t i o n o f r u b b e r i n s wo l l e n g e l V r，wh i c h was u s e d t o r e p r e s e n t t h e c r o s s l i n k i n g d e n s i t y o f t h e v u l c a n i z a t e s，wa s d e t e r mi n e d b y t h e e q u a t i o n V r=1 1+(m b m 一 1)P r l a 2 p ，Wh e r e m。a n d m b a r e t h e s a mp l e mass e s b e for e a n d a f t e r s we l l i n g，l0 a n d p a r e t h e d e n s i t i e s o f r u b b e r a n d s o l v e n t，r e s p e c t i v e l y，d i s t h e ma s s f r a c-t i o n o f r u b b e r i n t h e v u l c a n i z a t e s T r a n s mi t t e d e l e c t r o n m i c r o s c o p y(T EM)o b s e r v a t i o n s we r e p r e f o r me d wi t h a J E OL J EM 一 1 0 0 S X mi c r o s c o p e u s i n g a n a c c e l e r a t i o n v o l t a g e o f 8 0 k V Th e s a mp l e s we r e p r e p a r e d b y u s i n g a n u hr a mi c-r o t o me i n a l i q u i d n i t r o g e n t r a p M e c h a n i c a l t e s t i n g wa s p e r f o r me d a c c o r d i n g t o AS TM D 41 2 s t a n d a r d t o t e s t t h e s t r e t c h a b i l i t y，e l o n g a t i o n a t b r e a k a n d t e a r s t r e n g t hAl l t e s t s we r e me a s u r e d wi t h a S h i ma d z u AG I(J a p a n)S h o r e h a r d n e s s wa s me a s u r e d b y u s i n g a B a r e i s s Ro c k we ll t e s t e r a c c o r d i n g t o AS TM D一2 2 4 0 2 Re s t J l t s a n d d i$c tJ s s i o n 2 1 Th e a c t i v a t i o n e n e r g y of t he s y s t e m wi t h a d he-s i v e a c c e l e r a t o r PBS an d a c c e l e ra t o r CZ Th e r e i s a d h e s i v e s t r e n g t h b e t we e n mo n t