A simple and divergent synthetic strategy of bottlebrush polymers (BBPs) is presented, consisting of postpolymerization modification of a macromonomer and grafting‐through polymerization. Beginning with a single macromonomer, its direct modification could build a library of macromonomers with an identical chain length, thus guaranteeing the precision in the synthesis of BBPs. In this study, a newly designed norbornenyl‐terminated poly(methyl acrylate) (NB‐PMA) is proposed as a chemically robust template. Ti‐mediated transesterification of NB‐PMA successfully produces structurally diverse polyacrylates while maintaining the terminal norbornenyl group intact. All macromonomers obtained from transesterification possess a good grafting‐through ring‐opening metathesis polymerization reactivity, furnishing homo, random, and block BBPs in a controllable manner. Moreover, atomic force microscopy analysis supports the controlled side‐chain length distribution in the resulting BBPs.

中文翻译：

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通过大分子单体的后聚合改性合成瓶刷聚合物的不同策略

提出了一种简单多样的瓶刷聚合物（BBP）合成策略，包括大分子单体的后聚合改性和接枝聚合。从单个大分子单体开始，对其进行直接修饰可以构建具有相同链长的大分子单体库，从而保证BBP合成的精度。在这项研究中，提出了一种新设计的降冰片烯封端的聚丙烯酸甲酯（NB-PMA）作为化学稳健的模板。Ti介导的NB-PMA酯交换成功生产出结构多样的聚丙烯酸酯，同时保持末端降冰片烯基完整。从酯交换反应获得的所有大分子单体均具有良好的接枝-开环易位聚合反应活性，提供均一，无规，并以可控制的方式阻止BBP。此外，原子力显微镜分析支持所得BBP中受控的侧链长度分布。