CATIONIC HOMOPOLYMERIZATION OF ISOBUTYL VINYL ETHER AND SEQUENTIAL BLOCK COPOLYMERIZATION OF ISOBUTYLENE WITH ISOBUTYL VINYL ETHER - SYNTHESIS AND MECHANISTIC STUDIES

被引：42

作者：

HADJIKYRIACOU, S ^{[1
]}

FAUST, R ^{[1
]}

机构：

[1] UNIV MASSACHUSETTS,COLL ARTS & SCI,LOWELL,MA 01854

来源：

MACROMOLECULES | 1995年 / 28卷 / 23期

关键词：

D O I：

10.1021/ma00127a041

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The living polymerization of isobutyl vinyl ether (IBVE) and sequential block copolymerization of isobutylene (IB) with IBVE have been achieved using TiCl4 coinitiator in methyl chloride/ hexanes solvent mixtures in the -80 to -40 degrees C temperature range. Poly(IB-b-IBVE) with similar to 100% blocking efficiency has been synthesized for the first time. Close to 100% initiator efficiencies as well as 100% crossover efficiencies were obtained with 2,4,4-trimethyl-2-chloro-pentane (TMPCl) and PIBCl, respectively. The procedure involved capping with 1,1-diphenylethylene, followed by the addition of nBu(4)NCl to reduce the concentration of free, uncomplexed TiCl4 to [TiCl4](free) < [chain end] before the addition of IBVE. Mechanistic studies indicated that the presence of common ion salt is not necessary, and that living polymerization of IBVE and sequential block. copolymerization of IB with IBVE can also be accomplished in its absence when [TiCl4] ( [chain end]. It is proposed that under these conditions the gegenion is TiCl5-, a much stronger nucleophile compared to the Ti2Cl9- dimeric gegenion which dominates at [TiCl4](free)/[chain end] greater than or equal to 2.

引用

页码：7893 / 7900

页数：8

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