开环共聚法合成热可逆共价交联聚醚橡胶

SYNTHESIS OF THERMALLY REVERSIBLE COVALENT CROSSLINKED POLYETHER RUBBER BY RING- OPENING POLYMERIZATIO N

以烷基铝为催化剂，双环戊二烯二甲酸双缩水甘油酯为交联单体，与环氧氯丙烷、环氧乙烷、环氧丙烷进行离子型开环共聚，制得了热可逆共价交联的聚醚橡胶．研究了聚合方法、聚合配方和工艺条件对单体转化率、共聚物组成的影响．通过 Ｉ Ｒ 和 Ｄ Ｓ Ｃ 测定及反应溶解性和高温成型实验，证明了共聚物的结构及共价交联的热可逆转化特性．

Diglycidyl dicyclopentadienedicarboxylic acid ester( D G D C A) was used as acrosslinking monomer and was copolymerized with epoxide monomers, such asepichlorohydrin( E C H) ,by ring opening polymerization catalyzed by alkylaluminum system . The effects of polymerization procedure,feed ratio and reaction conditions on the monomerconversion and structure of the copolymer were studied in detail. It has been found that thecatalytic activity of Al Bu3 H3 P O4 N Et3 system was higher than Ali Bu3 acac Et O Et H2 Ocatalyst both in homopolymerization of E C Hand in copolymerization of D G D C A/ E C H,theproperties of reaction media have influence both on molecular weight of polymer and on theconversion ofcoplymerized monomer ,such asin homopolymerization of E C H,the [η] ofthepolymer have reached 4 9(d L/g) in toluene and only 0 954(d L/g) in n hexane under sameconditions ,butin copolymerization of D G D C A/ E C Hin n hexane ,the [η] ofcopolymer was5 11(d L/g) . And the conversion waslower down to 76 3 % . In addition the feeding orderof monomer and catalyst were almost haven’t influence on conversion and composition ofcopolymer, when the weight ratio of comonomer D G D C A/ E C H was controlled in 31 ～40 ,the conversion of most feeding order were higher than 90 % in cyclohexane as diluent andwhen E Oor P O was used instead of E C Hin copolymerization with D G D C Asimilar resultsand rules as above has been obtained . The structure and thermally reversible covalentcrosslinking properties of the obtained copolymers were confirmed by I R analysis and thetests ofreacting solubility , D S Cand pyrofluxibility .