异丁烯聚合新催化体系研究 Ⅰ.均聚与共聚反应

A Novel Catalyst System for IB Polymerization Ⅰ.Homopolymerization and Copolymerization

用苯甲酰氯 (BC) /TiCl4引发异丁烯 (IB)聚合及与苯乙烯 (St)的共聚反应 ,得到分子量高、分布窄的聚异丁烯及其共聚物 ,并控制了BC的高活性。对IB均聚及其与ST共聚反应影响因素 (体系浓度、残余水、第 3组分三乙胺 (TEA) )进行优化 ,得到最佳条件为 :[BC]=2 6mmol/L、[TEA]/[BC]=1 0 (均聚 )和n(TiCl4) /n(BC) =80、[TEA]/[BC]=4 0 (共聚 ) ,BC/TiCl4/TEA是最佳体系 ,对水不敏感 ,可以制备分子量高及分子量分布 (MWD)为 1 5 (均聚 )和 2 0 (共聚 )的窄分布聚合物 (GPC曲线均为单峰 )。

The catalyst system consisted of benzoyl chloride(BC), TiCl 4 and a third additive is developed to initiate polymerization of isobutene(IB) and its copolymerization with styrene(St). Polyisobutene(PIB) and PIB-PS copolymers of high molecular weight and narrow molecular weight distribution were obtained whereas the high activity of BC could be controlled effectively. Based on the examination of the effects of the catalyst concentration, residual water and the third additive(triethyl amine(TEA)) on the reaction activity, the optimized condition is obtained as: \=2.6 mmol/L and \/\=1.0 for homopolymerization and n(TiCl 4)/n(BC)=80 and \/\=4.0 for copolymerization. The BC/TiCl 4/TEA system is found to be the best optimal, it is characteristic of being insensitive to water. PIB with MWD=1.5 and P(IB-co-St) with MWD=2.0 were obtained(only single peak occurred in their GPC curves).