Organocatalyzed Controlled Radical Copolymerization toward Hybrid Functional Fluoropolymers Driven by Light

Photo‐controlled polymerizations are attractive to tailor macromolecules of complex compositions with spatiotemporal regulation. In this work, with a convenient synthesis for trifluorovinyl boronic ester (TFVB), we report a light‐driven organocatalyzed copolymerization of vinyl monomers and TFVB for the first time, which enabled the controlled synthesis of a variety of hybrid fluorine/boron polymers with low dispersities and good chain‐end fidelity. The good behaviors of “ON/OFF” switch, chain‐extension polymerizations and post‐modifications further highlight the versatility and reliability of this copolymerization. Furthermore, we demonstrate that the combination of fluorine and boron could furnish copolymer electrolytes of high lithium‐ion transference number (up to 0.83), bringing new opportunities of engineering high‐performance materials for energy storage purposes. A metal‐free controlled radical copolymerization of trifluorovinyl boronic ester and vinyl esters has been established, enabling the on‐demand synthesis of main‐chain hybrid functional polymers driven by light. This work furnishes a facile and versatile strategy to tailor F/B‐incorporated polymers, which facilitates chain‐extensions, post modifications to unprecedented polymers, and allows innovations of copolymer electrolytes.