Topology influences the properties and applications of polymers. Consequently, considerable efforts have been made to control topological structures. In this work, we have developed a photoorganocatalyzed divergent synthetic approach based on reversible‐deactivation radical polymerization (RDRP) that enables the preparation of both linear and branched fluoropolymers of low dispersity (Ð), a tunable degree of branching and high chain‐end fidelity by exposure to LED light irradiation under metal‐free conditions. This method promotes the generation of complicated structures (e.g., necklace‐like and mop‐like fluoropolymers) via chain‐extension photo‐RDRP, and provides a novel and versatile platform to access fluoropolymer electrolytes with high Li‐ion transference number and good ionic conductivity, which should create improved opportunities for advanced material engineering.

中文翻译：

---

光有机催化发散可逆失活自由基聚合成线性和支链含氟聚合物

拓扑影响聚合物的性质和应用。因此，已经做出了很大的努力来控制拓扑结构。在这项工作中，我们开发了基于可逆失活自由基聚合（RDRP）的光有机催化发散合成方法，该方法能够制备低分散度（Ð）的直链和支链含氟聚合物），通过在无金属条件下暴露于LED光照射下，可调节的分支度和高链端保真度。这种方法通过链延长光RDRP促进了复杂结构的生成（例如，项链状和拖把状含氟聚合物），并提供了一种新颖而通用的平台来访问具有高锂离子转移数和良好离子电导率的含氟聚合物电解质，这将为高级材料工程创造更多机会。