螺旋高分子的研究工作不仅可以探索生物大分子的螺旋结构和功能，而且可以开发出新的功能高分子材料。本项目拟发展新的钯催化剂，建立利用重氮单体可控聚合制备立构规整聚卡宾的新方法。通过手性单体可控均聚、手性单体与非手性单体(或外消旋体)可控共聚构筑螺旋手性聚卡宾，利用手性单体控制聚合反应的螺旋选择性，单体和催化剂的比例控制聚卡宾的分子量，从而可以获得具有特定螺旋结构和明确分子量的螺旋手性聚卡宾；拟设计合成新型的手性钯催化剂，利用手性催化剂引发非手性重氮单体(或外消旋体)活性聚合，通过催化剂的手性控制聚合反应的螺旋选择性，从而有望得到光学活性的螺旋手性聚卡宾。本项目中，我们还拟研究单体和催化剂的手性向聚卡宾螺旋主链的手性传递和放大效应，揭示手性传递和放大的基本规律。本项目的研究工作将为高分子科学领域发展新结构的螺旋高分子及其可控合成新方法；为材料科学领域提供新的手性功能高分子材料。

Study on helical polymer can not only explore the helical structure and related functions of biomacromolecules but also will develop novel functional materials. In this proposal, we will develop a series of novel palladium(II) catalysts for living/controlled polymerization of diazeacetates, through which we will establish a new method for controlled synthesis of stereoregular polycarbenes. Through living/controlled polymerization of chiral diazoacetates, and copolymerization of chiral monomer with achiral or racemic monomers, we try to synthesize optically active helical polycarbenes under controlled manner. In this case, the chiral monomer will determine the helicity, while the initial feed ratio of monomer to catalyst will control the molecular weights (Mns) and its distributions (Mw/Mns) of the resulting helical polycarbenes. Thus, helical polycarbenes with controlled handedness, tunable Mn and narrow Mw/Mn will be facilely obtained. Moreover, we will design and synthesize chiral Pd(II) catalysts to promote the controlled polymerizations of achiral or racemic diazoacetates. The chiral catalyst will determine the helicity of the resulting polymers, while the controlled polymerization will give polycarbenes with expected Mn and narrow Mw/Mn. Thus a series of helical polycarbenes with controlled helix and structures will be precisely prepared. Lastly, we will investigate the chiral transfer from monomer and catalyst to the helical main chain of polycarbenes, and will also investigate the chiral amplification during the polymerizations. Through these investigations, we try to disclose the general rules of chiral transfer and amplification during the diazoacetates polymerizations. On the basis of this project, we will not only develop a kind of new helical polymers and their controlled synthesis method, but also provide a series of novel functional materials for material science.