新型点击聚合体系探索及全取代1,2,3-三氮唑类序列定义聚合物的合成研究

Precise control of the sequential arrangement of monomer units in a polymer chain is one important part in the field of synthetic macromolecules, and has recently gained significant academic attention. The click reaction of copper-catalyzed azide-alkyne cycloaddition (CuAAC) plays an important role in the synthesis of sequence-defined polymers. However, due to the limitation in substrates scope, 1,4-disubstituted 1,2,3-triazoles are usually provided through CuAAC, and mostly utilized as linker of main chains or modification of side chains in polymers. Based on recently reported methods in organic synthesis, this project aims to develop new types of catalysis system for click polymerization, and referring to the structure of biomacromolecules, synthesize sequence-defined polymers with fully substituted triazoles (TA-SDPs) using 1,2,3-triazole as the main chain skeleton through rational designed strategies. Establishing monomer database, designing and synthesizing TA-SDPs for data storage and reading studies through precisely modular and programmed polymerization are another major research parts. Combined with theoretical calculation and simulation, we will further study the spatial topological structure of TA-SDPs, reveal the relationship between their structures and properties, which can provide information for potential function and application research. We hope this project can help to promote the study on sequence-defined polymer synthesis and applications, and enhance the research of macromolecule synthesis in our country.

精密控制单体在聚合物链中的序列排布是高分子合成领域的重要部分和研究前沿。铜催化的炔烃与叠氮的点击反应（CuAAC）是构建序列定义聚合物的重要方法之一。但受限于反应底物类型，CuAAC通常只能提供1,4-二取代-1,2,3-三氮唑，主要被应用于聚合物的主链链接体模块、侧链修饰等方面。本项目旨在基于新型有机合成方法，发展建立新型点击聚合催化体系，参比生物大分子，利用合理策略，控制合成以1,2,3-三氮唑为主链骨架的全取代三氮唑类序列定义聚合物（TA-SDPs）；建立可聚合单体数据库，通过模块化与程序化精密聚合，设计合成TA-SDPs并进行信息储存和读取等应用性研究；结合理论计算模拟，研究TA-SDPs的空间拓扑结构，揭示拓扑高分子结构与性质的关系规律，为潜在的功能和应用研究提供依据。最终希望本项目可以推动我国在序列定义聚合物的合成及应用方面的研究，促进提高我国高分子合成领域的研究水平。

精准合成新型高分子为多个研究领域提供重要素材，是高分子领域的重要研究前沿。该项目研究基于利用全取代三氮唑作为侧链载体的创新性思想，借鉴并发展IrAAC催化体系，通过合理策略，成功制备多种单一分子量的线性和支化序列定义高分子，主要包括：（1）通过合理设计硫炔单体，综合利用不同聚合增长策略，精准合成了一系列结构新颖的以三氮唑为侧链载体的序列定义聚合物，包括双序列定义聚合物、手性立构统一的聚合物、以及容易多官能团化和表征序列的寡聚物等；（2）通过发散或收敛增长策略，精准构筑了序列定义的内部官能团化树状大分子；（3）突破利用支化单元合成树状大分子的传统认知，基于硫炔类线性单元，经不对称增长策略合成了分子结构高度非对称支化的非传统树状大分子。并结合分子动力学模拟，研究了其空间拓扑结构，探索了其在信息储存、精密光学功能材料制备等方面的应用，为进一步的深入和拓展研究提供了重要依据和素材，可积极推动我国高分子精准合成领域的进展。

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