Organocatalyzed Controlled Radical Copolymerization toward Hybrid Functional Fluoropolymers Driven by Light

Angew Chem Int Ed Engl. 2022 Dec 23;61(52):e202215628. doi: 10.1002/anie.202215628. Epub 2022 Nov 24.

Abstract

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.

Keywords: Controlled Radical Polymerization; Copolymer; Fluorine; Photocatalysis; Synthetic Method.