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

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.

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。

高性能金属催化剂开发和功能聚烯烃制备始终是聚烯烃工业的两个重要方面。后过渡金属催化剂具有高活性和单活性中心的优点，且对极性基团具有好的耐受性，能实现极性环烯烃共聚。但目前研究的后过渡金属催化剂，由于配体结构缺乏构型设计导致其热稳定性差，且难以实现极性环烯烃共聚过程中对聚烯烃增长链的插入立构和性能控制。本研究借助分子设计，成功合成了系列新型具有C-C桥联限制几何构型β-酮亚胺或水杨醛亚胺镍、钯催化剂，以及具有空间立体几何构型α-二亚胺镍、钯催化剂，并通过单晶X-射线衍射测定确认了其C-C桥联限制几何构型和空间立体几何构型的结构。建立了一步原位合成C-C桥联[N^O]配位单金属催化剂的新方法，并弄清了原位C-C 桥联骨架构建的机制；在B(C6F5)3或MAO的活化下，高效实现了极性功能化降冰片烯的共聚合，制备得到了加工性能优异的降冰片烯及其衍生物类环烯烃共聚物，找出了催化剂几何构型与金属活性中心的配位环境开放性和亲电性之间的本质联系，建立了催化剂的分子设计合成-聚合物结构-材料形态与性能-应用的内在联系。通过动力学和共聚物序列结构的分析，弄清了共聚合的机理，找到了实现不同极性基团的功能化聚降冰片烯的结构和性能调控的规律。使极性功能化聚环烯烃的分子设计开发，理论上得到了合理的聚合机理，实践上能做到了聚合物结构和性能的调控。相关研究成果在Polym. Chem.、Journal of Polymer Science, Part A: Polymer Chemistry、RSC Advances等国际高水平SCI源刊物上发表学术论文6篇。获授国家发明专利1项，参加了国内相关学术会议3人次。共培养了6名硕士研究生毕业。本研究成果不仅拓宽了后过渡金属催化剂设计合成的思路，丰富了烯烃聚合催化剂的种类，而且还拓宽其在相关环烯烃共聚合以及环烯烃共聚物在新能源燃料电池和锂离子电池材料的应用领域。