聚合物载体-稀土金属络合物的表征及其催化聚合共轭双烯的活性

本文采用含一定量功能团的直链碳氢共聚物作为载体,如苯乙烯-丙烯酸共聚物(SAAC),苯乙烯-2-(甲基亚硫酰基)乙基甲基丙烯酸酯共聚物(SMC)。介绍了这类聚合物载体-稀土金属络合物的合成方法,讨论了它们的红外光谱。聚合物载体-钕络合物催化剂具有很高的催化活性和定向效应.SAAC·Nd 三元体系的催化效率高达170kg聚丁二烯/gNd·小时,SMC·NdCl_3 二元体系的催化效率是小分子氯化钕二甲基亚砜络合物 NdCl_3·4DMSO的 2—3倍。聚丁二烯顺式-1,4结构含量在 98％以上。体系也适用于异戊二烯的聚合,产物顺式-1,4含量在95％左右。

CHARACTERIZATION OF POLYMER-SUPPORTED RARE EARTH METAL COMPLEXES AND THEIR CATALYTIC ACTIVITY IN POLYMERIZATION OF CONJUGATED DIENES

In this paper linear hydrocarbon copolymers containing certain amount of function groups were used as the support such as styrene-acrylic acid copolymer (SAAC) and styrene-2-(methyl sulfinyl) ethyl methacrylate copolymer (SMC). The preparation of polymer-supported rare earth metal complexes (SAAC·Nd and SMC·LnCls) and their infrared spectra were described.The catalytic system formed from polymer-supported neodymium complexes shows high catalytic activity and stereospecificity for butadiene polymerization. The catalytic efficiency for SMC.NdCl₃-Al(i-C₄H₉)₃ system is twice or triple that of NdCl₃.4DMSO system. The cata-lytic efficiency of the ternary system,SAAC.Nd-Ph₃CCl-Al(i-C₄H₉)₃, reaches up to 170 kg polybutadiene/g. Nd.hr. The cis-1,4 content of polybutadiene is more than 98%. This system was also used for isoprene polymerization. The cis-1,4 content of the polyisoprene obta-ined is about 95%.