Post‐polymerization modification (PPM) is one of the most powerful strategy for preparing polymers with functional groups that cannot be synthesized by direct polymerization. So far, numerous experimental efforts have been devoted to the stability issue of monomer structures during the PPM process, but little attention was paid to chemical linkages. However, for hyperbranched polymers, a minor change of linkage unit could lead to a significant influence on the overall stability and performance of polymer materials. In this work, we investigated the chemical stability of long‐subchain hyperbranched polystyrenes with ester, aryl ether, and carbon‐carbon bonds as branching linkages under a few most popular PPM conditions, including NaOH hydrolysis reaction, TFA‐promoted hydrolysis reaction, BBr₃‐catalyzed methoxy‐hydroxyl conversion reaction, and LiAlH₄ carbonyl reduction reaction. Related results are summarized into a synthetic route map that can provide practical and intuitive guidance for preparing functional long‐subchain hyperbranched polystyrenes and other type of polymers by PPM for future applications.

中文翻译：

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后聚合改性制备功能性长亚链超支化聚苯乙烯：支化键化学稳定性的关键作用研究

聚合后改性 (PPM) 是制备具有无法通过直接聚合合成的官能团的聚合物的最有效策略之一。到目前为止，已经有大量的实验工作致力于 PPM 过程中单体结构的稳定性问题，但很少关注化学键。然而，对于超支化聚合物，连接单元的微小变化可能会对聚合物材料的整体稳定性和性能产生重大影响。在这项工作中，我们研究了以酯、芳基醚和碳-碳键作为支化键的长亚链超支化聚苯乙烯在一些最流行的 PPM 条件下的化学稳定性，包括 NaOH 水解反应、TFA 促进的水解反应、BBr ₃催化甲氧基-羟基转化反应和LiAlH ₄羰基还原反应。相关结果总结为合成路线图，可为未来应用 PPM 制备功能性长亚链超支化聚苯乙烯和其他类型聚合物提供实用和直观的指导。