(CH_3)_3SiCl/TiCl_4 INITIATING SYSTEM FOR CATIONIC POLYMERIZATION OF 1,3-PENTADIENE  

作　　者：彭宇行 

机构地区：[1]Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China

出　　处：《Chinese Journal of Polymer Science》1999年第5期459-464,共6页高分子科学（英文版）

基　　金：The National Natural Sciences Foundation of China is gratefully acknowledged for its financial support (grant No. 29504032)

摘　　要：Cationic polymerizations of 1,3-pentadiene (PD) initiated by trimethylsilyl chloride (TMSCl) incombination with TiCl_4 were carried out in n-hexane at 30℃. The yield of polymer was greatly increased bythe addition of TMSCl, indicating that the TMSCl/TiCl_4 combination is an efficient initiating system for PDcationic polymerization. However, the introduction of TMSCl gave rise to a drop in the molecular weight ofthe polymer. Kinetic results demonstrated that the polymerization initiated by TMSCl/TiCl_4 is 4.5 times fasterthan that induced by TiCl_4 alone. Various ethers were used to mediate the TMSCl/TiCl_4 initiating system.Adding diphenyl ether could increase both the yield and molecular weight of the polymer. Structural evidenceillustrates that the polymerization is indeed initiated by TiCl_4 in combination with HCl resulting fromhydrolysis by adventitious water.Cationic polymerizations of 1,3-pentadiene (PD) initiated by trimethylsilyl chloride (TMSCl) incombination with TiCl_4 were carried out in n-hexane at 30℃. The yield of polymer was greatly increased bythe addition of TMSCl, indicating that the TMSCl/TiCl_4 combination is an efficient initiating system for PDcationic polymerization. However, the introduction of TMSCl gave rise to a drop in the molecular weight ofthe polymer. Kinetic results demonstrated that the polymerization initiated by TMSCl/TiCl_4 is 4.5 times fasterthan that induced by TiCl_4 alone. Various ethers were used to mediate the TMSCl/TiCl_4 initiating system.Adding diphenyl ether could increase both the yield and molecular weight of the polymer. Structural evidenceillustrates that the polymerization is indeed initiated by TiCl_4 in combination with HCl resulting fromhydrolysis by adventitious water.

关 键 词：1 3-Pentadiene Cationic polymerization TMSCI TiCl_4 

分 类 号：TQ316.3[化学工程—高聚物工业]