钛酸酯、负载钛/三乙基铝体系引发异戊二烯聚合  

Polymerization of Isoprene Catalyzed by Titanates-TiCl_4/MgCl_2 and AlEt_3

作　　者：王鹏[1] 徐召来[1] 邵华锋[1] 姚薇[1] 黄宝琛[1] 

机构地区：[1]青岛科技大学橡塑材料与工程教育部重点实验室,山东青岛266042

出　　处：《青岛科技大学学报（自然科学版）》2010年第1期61-66,共6页Journal of Qingdao University of Science and Technology:Natural Science Edition

基　　金：国家自然科学基金资助项目(20674042)

摘　　要：以钛酸酯（Ti（OR）4）／三乙基铝（AlEt3）组成的单钛催化体系和钛酸酯、负载钛／（AlEt3）组成的复合钛催化体系引发异戊二烯（Ip）聚合。对比了钛酸正丁酯、钛酸正戊酯和钛酸正辛酯3种钛酸酯催化剂在不同聚合条件（钛酸酯用量、A1剂用量和反应温度）下引发Ip聚合时单体转化率的变化；研究了在复合钛催化体系下钛酸正丁酯用量和Al剂用量对单体转化率和催化剂效率的影响；并用FTIR、1HNMR和DSC对聚合产物进行了结构表征。结果表明：钛酸酯催化体系单独引发Ip聚合时，采用钛酸正丁酯催化体系的单体转化率较高，且钛酸酯的种类对聚合产物结构的影响不大，主要是3，4-结构；复合钛催化体系引发Ip聚合时，随着钛酸正丁酯／Ip（摩尔比）的提高单体转化率逐渐增加，而催化剂效率先增加后降低，较适宜的钛酸正丁酯／Ip为1．2×10^-3～1．6×10^-3。随着Al／钛酸正丁酯的增加单体转化率和催化剂效率均是先增加后降低，较适宜的Al／钛酸正丁酯为9～10。复合催化体系合成的聚异戊二烯结构主要是反式1，4结构和3，4-结构。Polyisoprene was synthesized using titanates-AlEt3 system and titanate-supported titanium-AlEt3 complex system as catalyst. When using Ti （C4H90）4, Ti （C3H11O）4 and Ti （C8H170）4 as catalyst,the effects of titanate dosage,Alt3 dosage and reac tion temperature on monomer conversion were investigated. When using titanate TiCl4/ MgCl2-AlEt3 complex as catalyst,the effects of Ti（C4 H90）4 dosage and AlEt3 dosage on monomer conversion and catalyst efficiency were also examined. The structure of ob tained polymer was characterized by FTIR,1H NMR and DSC. The results showed that the monomer conversion was higher using Ti（C4H90）4 AlEt3 as catalyst than that using Ti（C5 H11 O）4-AlEt3 or Ti（C8 H17 O）4-AlEt3 as catalyst. And the structure of the polymer obtained with titanates-A1Et3 catalyst is mainly 3,4-unit, different titanates has little effect on the structure of the polymer. When using titanate TiCL/MgCl2 A1Et3 complex as catalyst,with increasing of Ti （C4 H90）4/Ip （mole ratio） ,the monomer conversion increased, and catalytic efficiency increased at first and then decreased, and the appropriate Ti（C4H90）4/Ip was 1.2×10^-3--1.6 × 10-3. Both monomer conversion and catalytic efficiency increased at first and then decreased with increasing of Al/Ti（C4 H90）4, and the optimum Al/Ti （C4 H90）4 was 9-10. The polymer obtained with complex titanium catalysts is composed of trans-1,4- and 3,4-nuit.

关 键 词：钛酸酯 负载钛 三乙基铝 聚异戊二烯 

分 类 号：O632.14[理学—高分子化学] Q333.3[理学—化学]