聚合物载体－稀土金属络合物的研究Ⅺ．聚［苯乙烯－甲基丙烯酸β（甲基亚硫酰基）乙酯］载体－氯化钕络合物催化体系丁二烯聚合的动力学参数

STUDY ON POLYMER SUPPORTED RARE EARTH METAL COMPLEXES Ⅺ. KINETIC PARAMETERS OF BUTADIENE POL YMERIZATION WITH POLY[STYRENE-2-(METHYL SULFINYL) ETHYL METHACRYLATE] SUPPORTED NEODYMIUM CHLORIDE COMPLEX XYXTEM

采用膨胀计法，研究了以Ａｌ（ｉ－Ｂｕ）＿３为助催化剂，聚［苯乙烯－甲基丙烯酸β（甲基亚硫酰基）乙酯］载体－氯化钕络合物为主催化剂的丁二烯聚合动力学。丁二烯均聚时聚合速率对单体浓度和主、助催化剂浓度均呈一级关系，与氯化钕二甲基亚砜络合物－Ａｌ（ｉ－Ｂｕ）＿３体系基本一致，但前者的表现活化能仅为１８．７ｋＪ／ｍｏｌ，后者为４６９．ＫＪ／ｍｏｌ，前者的钕利用率大约是后者的５倍。

The kinetics of butadiene polymerization with the system of poly[styrene-2-(methyl sulfinyl)ethyl methacrylate]supported neodymium chloride (PSM·NdCl3) was studied by dilatometric method using Al(i-Bu)3 as cocatalyst.The rate of polymerization was first order to the concentration of monomer,Al and Nd.This was identical with that of neodymium chloride dimethyl sulfoxide complex (NdCl3·4DMSO)system on the whole.The apparent activation energies deter mined from two systems,PSM·NdCl3 and NdCl3·4DMSO, were 18.7 and 46.9KJ/mol respectively.The Nd utilization ratio of the former was about five times that of the latter.