极性单体与乙烯和双烯烃配位共聚合是实现聚乙烯塑料和聚双烯烃橡胶等通用材料功能化、高性能化的重要途径。该共聚反应的催化剂通常是Lewis酸性的过渡金属配合物，极性单体为Lewis碱，二者螯合作用使催化剂毒化，导致共聚活性、产物分子量、极性单体插入率等都非常低。解决上述问题是高分子科学前沿课题之一。最近我们发现极性基团可以“活化”催化剂并控制单体选择性。本课题拟设计与合成不同空间与电子效应的稀土催化剂，探索中心金属Lewis酸性与极性单体Lewis碱性对螯合作用强弱与可逆性、进而对催化活性的影响；研究极性基团的种类与取代位置对极性单体与活性种配位优势的影响、对极性与非极性单体中反应性双键竞争配位-插入的影响及立体选择性的控制；寻求改变单体间固有竞聚率、调节极性基团的插入率并控制其分布的途径。实现极性苯乙烯、极性共轭双烯烃和乙烯、苯乙烯和共轭双烯烃立体可控嵌段、梯度和无规共聚，并揭示机理。

Coordination polymerization of polar monomers with ethylene and conjugated dienes is one of the most efficient methods to realize functionalizing and high value-added commonly used polymer materials like polyethylene plastics and poly conjugated diene rubbers. However, the catalysts applied for this coordination copolymerization are usually Lewis acidic transition metals based complexes which are easily poisoned by the Lewis basic polar groups from the polar monomers owing to acid-base interaction, leading to low activity, low molecular weight and low polar group insertion. Thus the coordination polymerization of polar and nonpolar monomers is one of the most challenging projects of polymer science. Recently, we found that the polar group might activate the catalysts and control the stereo-regularity of the monomers. Based on this, in this project, we will design and synthesize a series of rare-earth metal complexes with various sterics and electronics, to explore the possibility of controlling the reversible chelating and the strength between the Lewis basic polar group and the Lewis acidic metal center, and thus influencing the catalytic activity; study the effects of the type and position of the polar substituents on the coordination privilege of the polar monomers to the metal centers and the competitive coordination of the active double bonds from polar and nonpolar monomers, as well as the selectivity; investigate how to vary the intrinsic reaction ratios of monomers to change the polar group insertion rates and their distribution along the polymer chains. Finally to realize the di- and tri-polymerizations of polar styrenes, polar conjugated dienes with ethylene, styrene and dienes to form the block, gradient, taper and random microstructure products, and to reveal the mechanism.