This article reports a chain‐growth coupling polymerization of AB difunctional monomer via copper‐catalyzed azide–alkyne cycloaddition (CuAAC) reaction for synthesis of star polymers. Unlike our previously reported CuAAC polymerization of AB _n (n ≥ 2) monomers that spontaneously demonstrated a chain‐growth mechanism in synthesis of hyperbranched polymer, the homopolymerization of AB monomer showed a common but less desired step‐growth mechanism as the triazole groups aligned in a linear chain could not effectively confine the Cu catalyst in the polymer species. In contrast, the use of polytriazole‐based core molecules that contained multiple azido groups successfully switched the polymerization of AB monomers into chain‐growth mechanism and produced 3‐arm star polymers and multi‐arm hyperstar polymers with linear increase of polymer molecular weight with conversion and narrow molecular weight distribution, for example, M_w/M_n ~ 1.05. When acid‐degradable hyperbranched polymeric core was used, the obtained hyperstar polymers could be easily degraded under acidic environment, producing linear degraded arms with defined polydispersity. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019

中文翻译：

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叠氮化物-炔烃双官能单体的链增长聚合：从核芯合成带有线性聚三唑臂的星形聚合物

本文报道了通过铜催化的叠氮化物-炔烃环加成反应（CuAAC）反应，AB双官能单体的链增长偶联聚合反应，用于合成星形聚合物。与我们先前报道的AB _n（n的CuAAC聚合  ≥2）在超支化聚合物的合成中自发地表现出链增长机理的单体，AB单体的均聚表现出一个共同但不理想的逐步增长机理，因为在线性链中排列的三唑基不能有效地限制Cu催化剂在聚合物种类。相反，使用包含多个叠氮基的聚三唑基核心分子成功地将AB单体的聚合转换为链增长机理，并产生了3臂星形聚合物和多臂超星形聚合物，聚合物分子量随转化率线性增加分子量分布窄，例如M _w / M _n 〜1.05。当使用可酸降解的超支化聚合物核时，所获得的hyperstar聚合物在酸性环境下很容易降解，从而产生具有确定的多分散性的线性降解臂。©2019 Wiley Periodicals，Inc.J.Polym。科学，A部分：Polym。化学 2019年