聚苯乙烯负载茂钛族催化剂的合成及制备反应过程的研究

Studies on the Syntheses of Polystyrene-Supported Metallocene Catalysts and the Action of Metallocene in the Prepared Process

采用悬浮法和溶液法将带有不饱和双键的金属茂钛族化合物与苯乙烯、二乙烯基进行共聚，分别合成了以聚苯乙烯为载体的键联型负载茂钛族催化剂．茂锆化合物比茂钛化合物容易与苯乙烯、二乙烯基苯共聚．同时，对加入金属茂钛族化合物的苯乙烯自由基聚合动力学用重量分析法进行了详细地研究，结果表明茂金属化合物不仅对ＡＩＢＮ的分解反应有促进作用，而且对苯乙烯自由基聚合的链式反应也有催化作用，茂钛化合物的催化作用比茂锆化合物的催化活性高，茂环上的取代基对茂金属化合物的催化活性影响较大，立体位阻小的催化活性高．茂锆化合物的催化反应类似与活性聚合，聚合反应中存在不同的活性中心。

Using suspension or solution polymerization,a series of supported titanium group catalysts were prepared by copolymerization of metallocene with unsaturated double bond substituent,styrene and divinyl benzene .Zirconocene compounds are easy copolymerized with styrene and divinyl benzene compared with titanocene. The influence of metallocene on the kinetics of styrene radical polymerization was investigated by conventional gravimetric methods.The results are shown that metallocene can not only catalyze the AIBN to decompose,but also accelerate the radical polymerization of styrene .The catalytic active of titanocene is greater than zirconocene .The substituent at the cyclopentadienyl has a great effect on the catalytic active of metallocene.The compound with less bulk substituent has great active .The polymerization under the zirconocene is different with simple radical reaction.The reaction has different active center and similar to living polymerization.