稀土配位催化环硫氯丙烷与环氧氯丙烷共聚合研究

Studies on the Copolymerization of Chloromethylthiirane with Epichlorohydrin by Rare Earth Coordination Catalysts

研究了稀土配位催化剂对难以开环均聚和共聚的环硫氯丙烷（ＣＭＴ）与环氧氯丙烷（ＥＣＨ）的共聚合。发现稀土乙酰丙酮盐、环烷酸盐等与异丁基铝、水组成的络合催化剂有良好的催化活性，能制备得到类交替共聚物，产率高达６０％以上，分子量颇高（［η］＝０．１５ｄＬ／ｇ）。应用ＩＲ、（１３）ＣＮＭＲ、ＧＰＣ、ＶＰＯ等测试手段对共聚物的结构和分子量进行了表征，测定ＣＭＴ（１）与ＥＣＨ（２）共聚合的竞聚率分别为ｒ１＝０．０２２、ｒ２＝０．０９７。

The copolymerization of chloromethylthiirane(CMT) with epichlorohydrin(ECH) was investigated by using rare earth coordination catalysts for the first time.It has been discovered that rare earth coordination catalysts,especially Nd (acac)3-Al(i-Bu)3 and Nd(naph)3-Al(i-Bu)3 are highly active catalysts for the copolymerization giving rather high molecular weight([η]=0. 16 dL/g) alternate-rich copolymer in fairly high yield(～60%),and the catalytic efficiency of Nd(acac)3-Al(i-Bu)3 reached 10 000 g copolymer/mol Nd. The characteristics of the copolymerization of CMT and ECH with Na(acac)3-Al(i-Bu)3 had been studied in detail.The reactivity ratio of CMT(1) and ECH(2) was obtained to be 0.22(r1) and 0. 097(r2) from the sulfur contents of the copolymers determined by oxygen combustion method.The structure and the molecular weight of copolymer were characterized by IR,13C NMR,GPC and VPO.