（α-二亚胺）镍催化剂聚集态的调控及其链穿梭聚合制备多嵌段支化聚乙烯的研究

In this project, the conjugation structure of the skeleton was used to cause the "π-π" accumulation of binuclear (α -diimide) nickel catalyst. The effects of solvent polarity, catalyst structure and polymerization conditions on the aggregation state of the catalyst were used to produce two very different active centers of "chain walking" capability. Through chain shuttling polymerization, a new type of polymer, multi-block branched polyethylene (MBBPE), was prepared with ethylene as the sole monomer, which provided a new idea for the preparation of thermoplastic elastomeric polyolefin by chain shuttling polymerization. Our preliminary research results indicate that MBBPE is a novel thermoplastic elastomer with excellent comprehensive performance. Its unique chain structure offers many unexpected properties. However, the polymerization mechanism and microkinetics of this catalyst, the regulation principle of the chain structure of MBBPE and the relationship between the structure and the properties of MBBPE remain to be further explored and revealed. Therefore, aiming at the novel catalytic system producing MBBPE, in this project a series of systematic research works including design and synthesis of catalysts with defferent structure , polymerization kinetics and mechanism, the relationship between the structure and the properties of MBBPE et al. will be carried out. It will lay a solid foundation for the practical application of MBBPE as a new type of thermoplastic elastomer. The research results of this project can be used not only to widen the application of chain shuttling polymerization and as a demonstration for preparation of novel polymer via chain shuttling polymerization, but also to enrich and improve the theoretical knowledge of polymer chemistry and physics. At the same time, this project will provide a novel polymeric material with unique properties. For these reasons, the research contents in this project have good academic value and application prospect.

本项目运用骨架的共轭结构造成双核（α-二亚胺）镍催化剂发生“π-π”堆积作用，利用溶剂极性、催化剂结构和聚合条件对催化剂聚集状态的影响，产生两种“链行走”能力差异很大的活性中心，通过链穿梭聚合，以乙烯为唯一单体制备一种新型的聚合物——多嵌段支化聚乙烯（MBBPE），为利用链穿梭聚合制备聚烯烃热塑性弹性体材料提供了新思路。MBBPE是一种综合性能优异的热塑性弹性体，其独特的链结构提供了许多意想不到的性能。本项目将针对这种合成MBBPE的新型催化聚合体系，开展从催化剂设计合成、聚合反应动力学与机理到聚合产物结构与性能的系统研究，为MBBPE这种新型热塑性弹性体的实际应用奠定坚实的基础。研究结果不仅可为拓宽链穿梭聚合的应用及通过链穿梭聚合制备新型聚合物做示范，还可以丰富和完善高分子化学与物理的理论知识，并提供具有独特性能的新型聚合物材料，具有很好的学术价值和应用前景。

本项目针对骨架共轭的双核（α-二亚胺）镍催化剂聚集状态的调控及其乙烯聚合规律研究、双核/单核（α-二亚胺）镍催化剂复合体系合成多嵌段支化聚乙烯的研究、通过改变双核（α-二亚胺）镍催化剂的结构调控其合成LBPE的性能、多嵌段支化聚乙烯的链结构表征与结构性能关系研究四方面内容开展了系统的研究工作。项目的开展使得我们掌握了骨架共轭的双核（α-二亚胺）镍催化剂的结构、乙烯链穿梭聚合条件与所得多嵌段支化聚乙烯的组成、链结构和性能间的关系，揭示了催化剂的聚合机理和微观动力学规律，初步掌握了调控多嵌段支化聚乙烯（MBBPE）链结构和物理性能的原理，探索了MBBPE这一类型的聚合物在太阳能电池封装胶膜、通用橡胶材料以及吸油材料方面的应用，这些研究结果和实验数据为开发高性能的MBBPE热塑性弹性体材料奠定了很好的科学和技术基础。