含轴向η6配位芳香环的α-二亚胺后过渡金属配合物的合成及制备链中官能化双烯烃聚合物

近年来，共轭双烯烃与极性双烯烃衍生物定向可控聚合制备官能化高顺式双烯烃合成橡胶引起了国内外学者的广泛关注。本项目以研制新型α-二亚胺后过渡金属催化剂为目标，通过引入轴向η6配位芳香环基团，增加活性中心对杂原子的耐受性，从而实现高活性、高选择性催化共轭双烯烃与极性丁二烯衍生物共聚，制备高性能官能化双烯烃合成橡胶。通过调节催化剂结构、共聚合条件、极性丁二烯衍生物种类等，筛选出最优的共聚合体系，并进一步制备一系列具有不同分子参数（顺1,4-含量、极性单体插入率、分子量、分子量分布等）的链中官能化双烯烃聚合物。通过核磁共振深入研究定量反应和聚合动力学，阐明双烯烃与官能化丁二烯衍生物共聚合机理。

Copolymerization of conjugated dienes and polar diene derivatives to prepare functionalized polydiene synthetic rubber has attracted a great deal of attention in the past few years. This project aims at development of novel α-diimine late transition metal complexes and their catalytic behaviors in copolymerization of dienes and polar diene derivatives. Through introducing axial η6 cooridinated aryl moiety to the ligand skeleton, the active species display a significantly enhanced tolerance towards different functional groups, and subsequently perform high activities and high stereoselectivities during the copolymerization process. The influence of various precatalyst structures, different polymerization conditions, and types of polar diene derivatives on polymerization behaviors are detailedly investigated in order to screen out an optimized polymerization system, which is further used to prepare a series of in-chain functionalized diene synthetic rubber with different polymer parameters, such as cis-1,4 content, comonomer incorporation, molecular weight, molecular weight distributions, etc. Possible copolymerization mechanisms are proposed based on kinetic and stoichiometric studies.