新一代高活性后过渡金属烯烃聚合催化剂  

Novel Highly Active Late Transition Metal Catalysts for Olefin Polymerization

作　　者：陈瑞芳[1] 钱长涛[1] 李杨[2] 邹丰楼 

机构地区：[1]中国科学院上海有机化学研究所,上海200032 [2]北京燕山集团有限化工公司研究院,北京100050

出　　处：《有机化学》2000年第5期712-718,共7页Chinese Journal of Organic Chemistry

摘　　要：介绍了近几年发展起来的新一代后期过渡金属(Fe,Co,Ni,Pd)烯烃聚合催化剂,对催化剂的结构、性能及催化烯烃聚合机理进行了阐述。The nickel (II) and palladium (II) systems coordinated by bulky diimine ligands are the first examples of late transition metal catalysts capable of polymerizing higher a - olefins as well as ethylene to high molecular weight polymers. The nickel(II)/MAO system can polymerize ethylene to produce a range of polyethylene materials with molecular weight up to 1 ×106 and degrees of branching from linear to over 70 branches per 1000 carbon atoms by simple variation of temperature, pressure, and ligand structures. The analogous palladium (II) complexes show moderate activity to produce very highly branched amorphous polyethylene. Furthermore, the palladium (II) catalysts are able to copolymerize a - olefins with functionalized monomers, including sulfonyl halide and carbonyl, resulting in highly branched random copolymers. In addition, A new family of complexes based on a five - coordinate iron or cobalt center supported by neutral tri-dentate2,6- bis(imino)pyridyl ligands and, when activated with MAO, shows exceptional high activity for ethylene polymerization. Activity figures in many cases are comparable or even higher than those found for Group 4 metallocene under analogous conditions. The molecular weight of the polyethylene material generated shows a marked dependency upon the aryl substitution pattern. Therefore, this review mainly covers families of late transition metal catalysts based largely on chelating nitrogen -based ligands that are active for homopolymerization of ethylene and the copolymerization of ethylene with a - olefins and polar monomers. Catalysts syntheses, structures, activities, and chain - growth mechanisms and the influence of these factors on the structures of the resulting polymers are also discussed.

关 键 词：后期过渡金属催化剂 烯烃 聚合 聚烯烃 催化性能 

分 类 号：O643.3[理学—物理化学]