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十五年前,我们曾首先报导了用镧系稀土化合物作为丁二稀的定向聚合催化剂,得到了顺-1,4-构型的含量高的聚丁二烯,这在Eiegler-Natta型催化剂中从利用d-轨道成键电子发展f-电子。当时所用催化剂为二元体系,后由Throckmorton改进成三元体系、聚合活性得以提高。之后,我们用三元体系对异戊二烯进行了定向聚合,也得到了顺式含量高的聚异戊二烯。近年来,我们对这类催化体系的定向性、催化聚合活性、聚合反应历程及动力学等方面,以及上述这两种均聚物在结构与性能方面的特点进行了研究。同时还发展了丁二烯和异戊二烯的共聚,两种链节的顺式含量都高,并在催化剂上从三元再发展到新的二元体系,其中一些代表性结果如下。
Fifteen years ago, we first reported the use of lanthanide rare earth compounds as butane diathesis polymerization catalysts, polybutadiene having a high cis-1,4-configuration content was obtained, which was obtained on an Eiegler-Natta type catalyst From the use of d-orbital bonding electrons develop f-electrons. At that time, the catalyst used was a binary system, which was improved to a ternary system by Throckmorton and the polymerization activity was improved. After that, we carried out the directional polymerization of isoprene with the ternary system and also obtained the polyisoprene with high cis content. In recent years, we have studied the orientation, catalytic polymerization activity, polymerization process and kinetics of these catalytic systems, as well as the structural and performance characteristics of these two homopolymers. At the same time, the copolymerization of butadiene and isoprene has also been developed. The cis content of the two kinds of chain links is high and has been developed from ternary to new binary system on the catalyst. Some of the representative results are as follows.