受生物大分子螺旋结构和功能的启发，人们对螺旋高分子产生了极大的研究兴趣。聚异腈是一种典型的螺旋高分子、具有良好的稳定性和广泛的应用前景。前期工作中，我们发展的炔钯配合物可以引发多种异腈单体活性聚合生成立构规整螺旋聚异腈。但是聚合后钯片段停留在聚异腈的末端上，性质稳定，难以转化和脱除。本项目中，我们拟在聚异腈末端钯上引入新的配体提高其反应活性，再通过钯催化的偶联反应将功能基团引入到聚异腈端基上，实现聚异腈端功能化和催化剂脱除；基于类似的原理，我们拟利用聚异腈与芳基单体共聚，将共轭高分子引入到聚异腈上，合成端功能化螺旋聚异腈，并研究共聚反应的可控性和单体普适性；利用聚异腈端功能化的方法，我们拟在聚异腈的首、尾两端引入反应性基团，通过端基间的反应制备超支化螺旋聚异腈，并探索其手性分离性能。本项目的研究工作将为端功能化螺旋聚异腈与超支化聚异腈的合成提供新的方法，为手性分离领域提供新的手性分离材料。

Inspired by the helical structures and the related functions of biomacromolecules, artificial helical polymers have attracted considerable research attentions in recent years. Polyisocyanide is a class of famous helical polymer owing to its stable helical conformation and a range of appealing applications. In our previous works, we have developed a family of alkyne-Pd(II) catalysts, which can initiate living polymerizations of various isocyanide monomers. However, the Pd(II) complex was located at the end-terminus of the generated helical polyisocyanide, which was too stable to be removed and the end-functionalization is difficult. In this proposal, we attempt to introduce various ligands to the end-Pd(II) unit of the helical polyisocyanides to enhance its reactivity. Thus a variety of functional groups can be installed onto polyisocyanide chain end through appropriate Pd(II)-mediated coupling reactions and simultaneously remove the residue Pd(II) catalyst. Based on the same mechanism, we try to copolymerize functional aryl monomers with the Pd(II)-terminated polyisocyanide to incorporate a conjugated polymer onto helical polyisocyanide chain end, which will lead to the formation of well-defined block copolymers containing helical polyisocyanide and functional conjugated polymers. We will study the controllability and the monomer scope of the block copolymerization. Taking advantage of the end-functionalization method, we will introduce reactive groups onto the two ends of helical polyisocyanide. Through the reactions of the head- and end-groups, we attempt to synthesize hyperbranched helical polyisocyanides, and explore their chiral resolution ability. Through these studies, we want to establish a method for facile synthesis of end-functionalized helical polyisocyanides and hyperbranched polyisocyanides, and develop new functional materials for chiral resolution.