Alkyl zinc chlorides as new initiators for the polymerization and copolymerization of isobutene

被引：11

作者：

Guerrero, Antonio ^{[1
]}

Kulbaba, Kevin ^{[1
]}

Bochmann, Manfred ^{[1
]}

机构：

[1] Univ E Anglia, Sch Chem Sci & Pharm, Wolfson Mat & Catalysis Ctr, Norwich NR4 7TJ, Norfolk, England

来源：

MACROMOLECULAR CHEMISTRY AND PHYSICS | 2008年 / 209卷 / 16期

基金：

英国工程与自然科学研究理事会;

关键词：

alkyl zinc complex; anion effect; carbocationic polymerization; copolymerization; initiators; isobutene; isoprene; zinc chloride;

D O I：

10.1002/macp.200800150

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Mixtures of RZnCl and tBuCl (R = Et) initiate the polymerization of isobutene in the temperature range of (- 35) - (+ 35) degrees C. The order of addition of the reagents is important for effective polymerization. Increasing the solubility of the zinc reagent (R = n-octyl) and use of cumyl chloride as co-initiator provides a system that is active from (-90) - (+35) degrees C. The molecular weights show a remarkably small temperature dependence, E-DP = -3.3 KJ.mol(-1), compared to E-DP = -23 kJ.mol(-1) in classical systems (AlCl3, EtAICl(2)). The molecular weights increase with decrease in zinc concentration and are consistently higher for n-octyl zinc chloride, as expected for a bulkier, less coordinating counteranion polymerizations are not retarded by isoprene addition; homopolymers and copolymers show essentially identical conversions and molecular weights.

引用

页码：1714 / 1720

页数：7

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[1] Dimethylaluminum chloride catalyzed living isobutylene polymerization [J].