Multicomponent Polymerization of Azides, Alkynes, and Electrophiles toward 1,4,5-Trisubstituted Polytriazoles

作者：Ming Li, Xuelun Duan, Yu Jiang, Xinhao Sun, Xiang Xu, Yubin Zheng, Wangze Song, Nan Zheng · 发表于：Macromolecules · 年份：2022 · DOI：10.1021/acs.macromol.2c00966 · 被引用次数：18 · 研究领域：Click Chemistry and Applications、Protein Degradation and Inhibitors、Chemical Synthesis and Analysis

As a model click reaction, alkyne–azide cycloaddition (AAC) has been widely applied in polymer and materials sciences. The corresponding alkyne–azide polymerization is a powerful approach for preparing polytriazoles with versatile functionalities such as antimicrobial activity, heat resistance, and metal coordination. However, it still remains a great synthetic challenge for the structural modification of polytriazoles due to the relative inert functional groups. Herein, inspired by the specific electrophiles in the interrupted AAC reaction to synthesize 5-functionalized triazoles, a multicomponent polymerization (MCP) using diynes, diazides, and electrophiles was developed, affording a library of 1,4,5-trisubstituted polytriazoles (1,4,5-PTAs) with high yields (up to 95%) and molecular weights (up to 280 100 g/mol). As the third component, five electrophiles were screened to optimize the ratio of 1,4,5-PTAs to non-functionalized 1,4-PTAs (up to 95% 1,4,5-PTAs were determined by 1 H NMR). To improve the solubility of the obtained products, diynes and diazides containing flexible chains were selected to prepare amphiphilic 1,4,5-PTAs, which could self-assemble into nanoparticles in water using the nanoprecipitation method. As nanocatalysts, such nanoparticles were further applied in the aqueous AAC reaction with excellent catalytic efficiency at a low Cu loading of 50 ppm. The introduction of the third component bearing chelating sites would stabilize Cu(I) under air condition...