新型聚乙烯弹性体导向的α-二亚胺镍配合物催化剂的研究进展  

α-Diimine nickel complex precatalysts for novel polyethylene elastomers

作　　者：张秋月 闫国春[2] 王建立[2] 李艺[2] 张世杰[2] 王权超 马艳平[1] 孙文华[1] ZHANG Qiuyue;YAN Guochun;WANG Jianli;LI Yi;ZHANG Shijie;WANG Quanchao;MA Yanping;SUN Wenhua(Key Laboratory of Engineering Plastics,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China;China Shenhua Coal to Liquid and Chemical Co.,Ltd.,Beijing 100011,China)

机构地区：[1]中国科学院化学研究所中国科学院工程塑料重点实验室,北京100190 [2]中国神华煤制油化工有限公司,北京100011

出　　处：《石油化工》2024年第4期463-488,共26页Petrochemical Technology

摘　　要：乙烯与α-烯烃共聚所制备的聚烯烃弹性体是聚烯烃材料的热点,可广泛应用于塑料相容剂、鞋底基材、光伏封装胶膜、微电子封装材料和弹性体纤维等高附加值产品领域。在我国缺少α-烯烃单体的形势下,迫切需要跨越传统共聚体系的新型催化剂。Brookhart型α-二亚胺镍(Ⅱ)配合物催化剂能够实现单一乙烯聚合制备聚乙烯弹性体,是特别值得重视和推进产业化的催化剂体系。该类催化剂在催化乙烯聚合过程中采用“链行走”机理,“通过调控催化剂结构,不仅可以调节催化活性,更重要地可实现对所得聚乙烯支链的有效剪裁”;这些微观结构可控的聚乙烯弹性体在具有窄分子量分布特点的基础上,涵盖了从低分子量(降凝剂)、中等分子量(膜材)到高分子量(高强度树脂)各个范围的聚合产物。综述了可制备乙烯低聚物,油性低分子量、中等分子量、高分子量甚至超高分子量全系列支化聚乙烯的α-二亚胺镍(Ⅱ)配合物的最新结构演变进展,对结构的改性包括N-芳基取代基的修饰、配体骨架结构的修饰和双核配体的利用三个部分;从空间效应和电子效应两方面探讨了配合物结构与催化性能的关系。α-二亚胺镍(Ⅱ)催化剂合成简单,具有中试放大基础和产业化推进的潜能,为单一乙烯聚合制备多品种新型聚乙烯弹性体奠定了良好基础。The polyolefin elastomer prepared by the copolymerization of ethylene andα-olefins has become a hot competition for polyolefin materials,as it can be widely used in high value-added product fields such as plastic compatibilizers,shoe sole substrates,photovoltaic packaging films,microelectronic packaging materials,and elastic fibers.In the current absence ofα-olefin monomers in China,there is an urgent need for innovative catalysts to transcend traditional copolymerization systems.The Brookhart typeα-diimine nickel(II)complex can use sole ethylene monomer to prepare polyethylene elastomers,becoming a catalyst system that deserves special attention and promotion of industrialization.This type of catalyst adopts the“chain walking”mechanism in the polymerization,which can achieve“through finely turning the(ligands’)structures of complexes,the catalytic systems could be achieved with not only adjusting the catalytic activity but also importantly and effectively tailoring their branches of resultant polyethylenes”.These polyethylene elastomers with controllable microstructure,based on their narrow molecular weight distribution,can cover polymerization products ranging from low molecular weight(pour point depressants),medium molecular weight(membrane materials)to high molecular weight(high-strength resins).This review summarizes the latest structural evolution progress ofα-diimine nickel(II)complexes which can deliver oligomers,oily low molecular weight,medium,high,and even ultra-high molecular weight branched polyethylene in a full range.The structural modification in this review includes three parts:N-aryl substituents,ligand skeleton structure,and utilization of binuclear ligands.The relationship between complex structure and catalytic performance is explored from two aspects:steric and electronic effects.Theseα-diimine nickel(II)catalysts are simple to synthesize and have the potential for pilot scale up and industrial promotion,laying a good foundation for the preparation of multiple new-type polyeth

关 键 词：α-二亚胺镍配合物 链行走机理 乙烯低聚 乙烯聚合 聚乙烯弹性体 

分 类 号：TQ325.1[化学工程—合成树脂塑料工业]