梯度、多嵌段及非线性拓扑结构高分子材料具有丰富的相态和聚集态及优异的物理性能，其合成与应用一直是高分子科学的研究热点。经典的合成方法是阴离子和活性自由基聚合与“点击”化学等偶联反应相结合。本项目将应用配位聚合机理，以质子化合物为链转移剂，构筑“不死聚合”体系，简单、高效、原位合成立构规整的这些材料。将设计与合成具有立体选择性的金属有机配合物，研究其与链转移剂（醇或胺化合物）进行可逆-快速交换反应的关键因素：配体的结构及与链转移剂之间的Lewis酸性匹配、金属σ-基团的种类和离去能力，对构筑“不死聚合”体系的影响。研究不同立体选择性的催化剂并联、借助质子化合物导向的“链穿梭”作用，制备梯度和多嵌段聚酯，揭示催化剂间相对活性、单体与链转移剂的比例和加入方式与嵌段长度及分布的规律。探索以多官能度链转移剂为模板，或羟基/胺基修饰的内酯开环聚合与“不死聚合”的协同作用，制备拓扑结构聚酯的途径。

The synthesis of gradient, multi-block and topologic polymer materials having versatile morphologies and aggregation states as well as excellent physical and mechanical and rheological properties, has been the hot research topics and challenging projects in polymer science. The classical method to access such materials is the combination of living radical and anionic polymerizations with organic reactions such as “click reaction” and coupling reactions. In this project, the coordination polymerization will be employed to combine with chain transfer agents of protic compounds to establish catalytic systems, thus the stereoregulated such materials will be achieved facilely and efficiently in situ. First, the organometallic complexes with stereo selectivity will be synthesized, and the factors, such as the structures of the ligands and the match of Lewis acidity between the ligands and the chain transfer agents, the metal-σ-groups and their leaving ability, which influence the rapid-reversible exchange reaction between these complexes and alcohols or amines to access the “immortal” polymerization, will be studied. Two complexes of different selectivity towards polymerization of cycloesters under the action of the chain-shuttling agents to achieve the gradient and multiblock polymers, will be investigated. The effects of the catalytic activity of the added two complexes, the molar ratio of the chain shuttling agents with the monomers and the addition manner of the monomers on the block lengths and their distribution, will be addressed. Preparation synthon of the topological polymer materials taking the multi-functional chain transfer agents as the templates, or the concert effect of the ring-opening polymerization and immortal polymerization of the hydroxyl or amino modified cyclic esters, will be elucidated.