Friedel－Crafts反应合成无规支化聚苯乙烯及其支化结构表征

Preparation of Atactic-branched Polystyrene by Friedel-CraftS Reaction and Characterization of its Branching Structure

将阴离子聚合所得窄分布聚苯乙烯（ｄ＜１．１）在无水ＺｎＣｌ＿２催化下以氯甲醚对其进行氯甲基化（Ｃ１％＜１．５），再用自制无水ＡｌＣｌ＿３作催化剂，使氯甲基化聚苯乙烯（ＣＭＰＳ）发生大分子链间的Ｆｒｉｅｄｅｌ－Ｃｒａｆｔｓ反应，一步合成主链与支链等长的无规支化聚苯乙烯（ＡＢＰＳ）．研究了支化反应条件及支化结构，实验表明，反应条件：Ｔ＝４０～４５Ｃ、Ｃ＿（ＣＭｐＳ）＝０．１～０，１５ｇ·Ｍｌ￣（－１）、Ｃ＿（ｃａｔ）＝０．０５～０．１ｇ·ｍｌ￣（－１）、ｔ＞ｌ２ｈ达到良好的支化效果，支化臂数为１～２０．

Narrow molecular distribution polystyrene(d<1.1) self-prepated by anionicpolymerization can be chloromethylated by chloromethyl ether when catalyzed by anhydro zincchloride. The products,chloromethylation polystyrene (CMPS)with chlorine content less than1.5%,were catalyzed by anhydro alumium chloride to lead Friedel-Crafts Reaction to take placeamong defferent molecules of themselves. Target products,atactic branched polystyrene(ABPS),were so synthesized.Branching conditions and structure were also investigated to show that thefollowing conditions:T=40～45℃,C_(CMPS)=0.1～0.15 g·ml￣(-1),C_(cat)=0. 05～0.1 g·ml￣(-1),t>12 h were the optium to get expected products. The number of branching arms averaged from one to twenty.