钛系催化剂合成顺-1，4-聚异戊二烯的研究论文.pdf

青岛科技大学硕士学位论文钛系催化剂合成顺-1,4-聚异戊二烯的研究姓名:王曙光申请学位级别:硕士专业:高分子化学与物理指导教师:宗成中 20070418 青岛科技大学研究生学位论文钛系催化剂合成顺一1,4一聚异戊二烯的研究摘要钛系催化剂是催化异戊二烯聚合的一种工业上常用的催化剂。本实验以面Ch-Al(】3为催化剂,在加氢汽油中合成了高顺式l冉聚异戊二烯。讨论了催化剂各组份用量、单体浓度、反应温度等对聚合的影响,得出最佳工艺: [单]/[油]=1/4(体积比),n(Ti)/n(Ip)=2xlo-3,n(AI)/n(Ti)=1,反应温度50 ℃,测得聚合物的顺1,d-结构含量在96%以上,·g-l,凝胶含量为5%。 TiCh-Al()3-DPE三组分催化体系亦可制备具有高顺式含量的聚异戊二烯。对体系中三组分催化剂络合方式、各组分用量等对聚合的影响进行了研究。结果表明,改性后的催化剂制得聚合物的顺式含量提高,-%。三种组分单独加入反应体系中,在 n(DPE)/n(A1)----。()-Ti络合方式和AI-(DPE-Ti)络合方式,。采用TiCi4-AI(i-Bu)3-AICl3三组份催化体系制备的聚异戊二烯不含反式1^结构,顺式l,4一链节含量为96%左右。研究了三组分催化剂铝钛摩尔比、催化剂浓度、反应温度等对聚合的影响,n(A1)/n(Ti)在1~6之间均可得到顺式聚异戊二烯。高温(80℃)下异戊二烯聚合时,n(Ti)/n(Ip)ffil×10"3,n(A1)/n('I])--.4时催化剂的催化效率最高,每克Ti可制得聚异戊二烯1589,聚合转化率为44%。低温预制催化剂,~60℃制得的催化剂活性最高,且低温制得的催化剂可以使聚合物凝胶含量降低。关键词: ',4-聚异戊二烯的研究 STUDY ON POLYMERIZATl0N OF WITH TITANIUM CATALYST ABSTRACT Ⅲ眦i眦catalyst monly used forpreparation with highcis-lA content was obtained by atwofold posed plex 骶C14 andAl(i—Bu) solution ofpolyisoprene pounded inhydrogenated effectofmonomer ratiosandanotherconditions ofpolymerization were discussed ,4 content of96%,【rl】of ’g。1 and gelcontentof 5%was obtained byTiCh-Al(i—Bub system under the following conditions:【Ip]/[Oil]=1/4(volume ratio),n(Ti)/n(Ip)=2x10。,n(A1)/n∞)=1,50"C polymerized for4hr. 碰gh cis- content Polyisoprene was alsoobtained essfully by a ternary catalytic system面Ch-A10-Bu) plex orders ponent dosage were couldimprove cis-1,4contentof polyisoprene meanwhilepolymer with cis-1,4contentof %was content ofpolyisoprene prepared bycatalyticsystem伽-DPE).Ti andAl-(DPE-Ti) was reduced. Polyisoprene withcis-contem of 96%was obtainedby catalytic system Ti04-Ala3-Al(i—Bu) effect of Al厂n mole concentrationand