Photocontrolled cationic polymerization of fluorinated vinyl ethers

Fluorinated polymers have been widely used in many fields, by virtue of their unique properties and excellent performances. The application of photopolymerization methods has further expanded the accessibility and application scope of fluorinated polymers. Herein, we report the development of a photocontrolled cationic polymerization of fluorinated vinyl ethers, which is enabled by employing a bisphosphonium-type photoredox catalyst. This method features metal-free conditions, low-energy visible light regulation, good livingness, and excellent temporal control over chain growth, which allow for the synthesis of fluorinated polymers with controlled molecular weight, variable fluorine content, and high chain-end group fidelity under mild conditions. Further synthesis of fluorinated di- and tri-block copolymers with tunable properties via this photopolymerization method is also demonstrated.