1,3-戊二烯阳离子聚合过程中环化反应的研究  

STUDY ON THE CYCLIZATION DURING THE CATIONIC POLYMERIZATION OF 1,3 PENTADIENE

作　　者：彭宇行[1] 刘佳林[1] 戴汉松[1] 寸琳峰[1] 

机构地区：[1]中国科学院成都有机化学研究所

出　　处：《高分子学报》1997年第1期19-24,共6页Acta Polymerica Sinica

基　　金：国家教委留学回国人员基金

摘　　要：以ＡｌＣｌ３和（ＣＦ３ＳＯ３）３Ａｌ为引发剂，ＣＨ２Ｃｌ２为溶剂，在２０℃聚合了１，３戊二烯（ＰＤ）．对聚合物（ＰＰＤ）的结构分析表明，（ＣＦ３ＳＯ３）３Ａｌ生成的聚合物具有较高的环化度．聚合物的环化过程是通过两种机理，分子内链转移机理和阳离子引发机理，后者可以通过加入ＤｔＢＰ得到抑制．ＡｌＣｌ３引发的聚合反应中环化过程以前一种机理为主，而（ＣＦ３ＳＯ３）３Ａｌ则以后一种机理为主．通过阳离子引发的环化反应主要发生在ＰＰＤ１。Pentadiene was polymerized in CH 2Cl 2 at 20℃,initiated by AlCl 3 and (CF 3SO 3) 3Al.The polymer chain contains both linear segments and cyclic structures.The cyclic fractions of PDD prepared by AlCl 3 and by (CF 3SO 3) 3Al are respectively 25% and 48%.The cyclization reaction takes place through two processes:(Ⅰ)Intramolecular chain transter;(Ⅱ)protonic initiation.The process(Ⅱ)could be essentially hindered in the presence of DtBP.The cyclization of PPD induced by AlCl 3 occurs mostly through the process (Ⅰ) and the cyclization in the polymerization initiated by (CF 3SO 3) 3Al is induced mainly by the process (Ⅱ).In the process (Ⅱ) the cyclization takes place on the double bonds of the lateral groups of 1,2 units.

关 键 词：戊二烯 阳离子聚合 环化聚合 聚戊二烯 

分 类 号：O632.14[理学—高分子化学]