基于稀土金属催化的含杂原子单体的聚合反应研究

Rare-earth metallocene catalyzed polymerization is an efficient synthetic method in obtaining functional polymers. However, the applicable scope of the polymerization is confined to nonpolar olefins and few polar monomers such as acrylates, acrylonitrile and lactones. From the point of structural design, this project aims to synthesize mono-nuclear lanthanocene complexes and explore the application of the as-synthesized catalysts in the polymerization of hetero-atom, i.e. nitrogen, phosphorus and sulfur containing monomers, to achieve the controlled polymerization of polar monomers which cannot be efficiently polymerized by classical polymerization techniques, obtaining a series of hetero-atom containing polymers with topological structures. The initiating, propagating and terminating processes involved in the polymerization will be systematically investigated by tuning the type of the metal center and the structure of ligands, and by mechanistic studies of the polymerization as well, thus to reveal the relationship between the structure of catalysts and properties of the obtained polymers, which will further provide theoretical and experimental data for the understanding of the polymerization of polar monomers catalyzed by lanthanocenes.

稀土茂金属催化聚合是一种获得功能高分子的有效方法，但该聚合方法的适用范围仍局限于烯烃类非极性单体，以及丙烯酸酯、丙烯腈、内酯等少数极性单体。本项目拟从结构设计角度出发，合成系列单核稀土茂金属配合物，探索该类型催化剂在含氮、磷、硫等杂原子单体聚合中的应用，实现传统方法难以突破的杂原子单体的可控聚合，获得系列具有拓扑结构的含杂原子聚合物。通过对催化剂的金属中心类型、配体结构的调控和聚合反应研究，明确该聚合反应的链引发、链增长与链终止过程，进而阐明催化剂结构、聚合物微纳结构和性能之间的关系，为进一步理解稀土茂金属催化的极性单体聚合提供新的理论与实验数据。

稀土茂金属催化聚合是一种获得功能高分子的有效方法，但该聚合方法的适用范围仍局限于烯烃类非极性单体，以及丙烯酸酯、丙烯腈、内酯等少数极性单体。本项目从结构设计角度出发，设计合成了系列单核稀土茂金属配合物，探索了该类型催化剂在含氮、磷等杂原子单体聚合中的应用，实现了传统方法难以突破的杂原子单体的可控高效聚合，进一步获得了系列具有线性以及拓扑结构的含杂原子聚合物（刷）。通过对催化剂的金属中心类型、配体结构的调控和聚合反应研究，明确该聚合反应的链引发、链增长与链终止过程，进而阐明催化剂结构、聚合物微纳结构和性能之间的关系，为进一步理解稀土茂金属催化的极性单体聚合提供了新的理论与实验数据。进一步工作中，我们还利用所制备聚合物(刷)实现了其在催化、纳米材料制备与光热疗法方面的应用。