Organocatalyzed Controlled Copolymerization of Perfluorinated Vinyl Ethers and Unconjugated Monomers Driven by Light

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Perfluorinated vinyl ethers (PFVEs) are an important category of monomers for producing fluoropolymers that have found broad applications. In this work, by developing a dibenzo[ a, c ]phenothiazine-based organic photoredox catalyst, we realize photo-controlled radical copolymerization of various PFVEs and unconjugated comonomers (e.g., vinyl esters, vinyl amides, and vinyl ethers) with a high reaction efficiency when exposed to visible-light irradiation, affording a large series of main- and side-chain fluorinated copolymers of low dispersities ( D̵ = 1.06–1.24) and good chain-end fidelity at excellent conversions of unconjugated comonomers. Furthermore, this method not only facilitates the “ON/OFF” temporal switch of the chain growth with tunable kinetics for the “ON” states upon altering the wavelengths of light sources but also allows photo-controlled chain extensions with copolymers and homopolymers as additional blocks, presenting a facile and versatile platform to customize complex fluoropolymers for material engineering.