基于功能环烯烃共聚的C-C桥联[N^O]配位单金属限制几何构型催化剂一步原位构筑、构-效关系及机理

项目名称： 基于功能环烯烃共聚的C-C桥联[N^O]配位单金属限制几何构型催化剂一步原位构筑、构-效关系及机理

项目编号： No.21674045

项目类型： 面上项目

立项/批准年度： 2017

项目学科： 数理科学和化学

项目作者： 贺晓慧

作者单位： 南昌大学

项目金额： 32万元

中文摘要： 高性能金属催化剂和功能聚烯烃研发始终是聚烯烃工业的两个重要方面。借助分子设计及过渡金属催化C-H键活化/C-C键偶联反应策略，一步原位构筑高效、稳定的C-C桥联[N^O]配位镍、钯单金属限制几何构型催化剂，探寻其对功能环烯烃共聚合构-效关系及机理。通过不同反应条件对C-C键偶联反应影响的研究，弄清原位C-C桥联骨架的构建机制，建立一步原位构筑C-C桥联[N^O]配位单金属限制几何构型催化剂的新方法；通过配体电子及位阻效应、中心金属等对催化剂结构、性能影响的研究，建立配体结构与金属中心配位模式、晶体结构的关系；通过不同催化剂对功能环烯烃共聚活性、共聚物结构、性能影响的研究，建立共聚活性、共聚单体插入率及序列分布与催化剂的构-效关系，获得高性能催化剂及体系；通过反应动力学和共聚物序列结构研究，弄清环烯烃共聚合机理，找到实现对聚环烯烃链结构与性能的调控规律，制备加工性好的功能化环烯烃共聚物材料。

中文关键词： 烯烃聚合催化剂；配位共聚合反应；分子设计；镍配合物；功能化聚烯烃

英文摘要： Research and development of high performance metal catalysts and functional polyolefin are always two important aspects of polyolefin industry. By means of molecular design and the strategy of transition metal catalyzing C-H bond activation and C-C bond coupling reaction, efficient and stable constrained-geometry-configuration(CGC) catalyst of C-C bridged [N^O] coordination Nickel or Palladium single metal will be constructed by one-step in situ method. The structure-activity relationship and mechanism for functional cycloolefin copolymerization will be explored and functionalized cycloolefin copolymer with good processability will be prepared. In situ construction mechanism of C-C bridged skeleton will be clarified by studying the effect of different reaction conditions on C-C bond coupling reaction, And a new synthesis method of C-C bridged [N^O] coordination single metal CGC catalyst via one-step in situ construction will be established. Through studying the electronic and steric effects of ligand structures as well as central metal on the influence of catalyst structure and performance, the relationship between ligand structure and metal coordination mode along with crystal structure will be established. Structure-activity relationship between catalyst structure and copolymerization activity, comonomer insertion rate and sequence distribution will be established，and high performance catalysts and catalytic systems will be obtained by studying the different catalysts structures on the copolymerization activity of functional cycloolefin and the structure and properties of functionalized copolymer. Copolymerization mechanism of cycloolefin will be understood and controllable law of copolymer chain structure and properties will be achieved by studying reaction dynamics and the copolymer sequence structure.

英文关键词： Olefin polymerization catalyst;coordinative copolymerization reaction;molecular design;nickel complex;functional polyolefin