三甲基硅化合物复合体系引发1,3-戊二烯阳离子聚合研究  

CATIONIC POLYMERIZATION OF 1,3-PENTADIENE INITIATED BY TRIMETHYSILYL COMPOUNDS INITIATING SYSTEMS

作　　者：邓建国[1] 彭宇行[2] 

机构地区：[1]中国工程物理研究院化工材料研究所,绵阳621900 [2]中国科学院成都有机化学研究所,成都610041

出　　处：《高分子学报》2001年第3期293-298,共6页Acta Polymerica Sinica

摘　　要：研究了三甲基硅化合物 ,主要是三甲基硅酯和三甲基硅氯化物 (TMSCI)与路易斯酸所形成的复合引发体系引发聚合 ,1,3 戊二烯 (PD)的聚合反应行为 ,考察了引发体系引发PD聚合所得聚合物的产率 ,分子量及分子量分布 ,聚合反应速率和聚合反应机理等 ;研究了多种给电体———醚。Cationic polymerization of 1,3\|pentadiene initiated by trimethylsilyl compounds, trimethysilyl trifluoromethanesulfonate (TMSOTf) or trimethysilyl chloride (TMSCl), in combination with TiCl 4, SbCl 3 or AlCl 3 was carried out in n \|hexane or in toluene. The polymer yields are greatly increased by the addition of TMSOTf or TMSCl. However, the introduction of TMSOTf or TMSCl gives a drop of polymer molecular weight. Kinetic results demonstrate that the polymerization initiated by the composite initiating systems is faster than that induced by Lewis acids alone. Various electron donors (such as ethers, ketones) were used to mediate the initiating systems. Adding diphenyl ether could increase both polymer yield and molecular weight. Structural evidences illustrate that the polymerization is initiated by Lewis acid in combination with HCl or HOTf, which are resulted from hydrolysis of TMSCl or TMSOTf by water contained in the system.

关 键 词：1 3-戊二烯 复合引发体系 三氟甲基磺酸三甲基硅酯 三甲基氯硅烷 阳离子聚合 

分 类 号：O631[理学—高分子化学]