新型镍催化体系合成Cis-1,4聚丁二烯的研究

STUDY OF THE SYNTHESIS OF Cis-l,4-POLYBUTADIENE WITH NEW NICKEL CATALYST SYSTEM

本文研究了以加氢汽油为溶剂的Ni(Naph)_2-Al(i-Bu)_2OR-BP_3·OEt_2及Ni(NaPh)_2-Al(i-Bu)_2OAr-BF3·OEt_2两体系对丁二烯的催化聚合活性、聚合物分子量、微观结构等。各种Al(i-Bu)_2OR或Al(i-Bu)_2OAr为助催化剂组成的新型镍催化体系对丁二烯聚合都有较高的催化活性,所得聚合物Cis-1,4含量在96％以上。磁化率和紫外可见光谱研究证明,在Al(i-Bu)_2OR体系中以Ni(Ⅰ)为主及小量未还原的Ni(Ⅱ);Al(i-Bu)_2OAr中Ni(Ⅰ)及Ni(O)共存。

The catalytic activity of Ni-Al(i-Bu), OR-B and Ni-Al(i-Bu)2 OAr-B system (-OR is -OC8H17, -OC9H19 and -OAr is -O-Ph-CH3, -O-Ph-C8H17) for the polymerization of butadiene in hydrogenated dasoline, the modecular weight of the polymer, and the micros tructure of the polymer have been studied. The result showed that the catalytic activity of the new nickel catalpst system for the polymerization of butadiene is very high when the co-cata-lyst is Al(i-Bu)2OR or Al(i-Bu)2OAr, and that the content of Cis-1,4 unit in polymer prepared is about 96%. Based on the mapnetic susceptibility measurement and OW-VIS spectum of the new nickel catalst systems, it could be seen that the Ni(I) existed mainly in the Al(i-Bu)2OR system, and the Ni(I) and Ni(0) coexisted in the Al(i-Bu)2 OAr system.