Main-Chain Fluoropolymers with Alternating Sequence Control via Light-Driven Reversible-Deactivation Copolymerization in Batch and Flow

Polymers with regulated alternating structures are attractive in practical applications, particularly for main-chain fluoropolymers. We for the first time enabled controlled fluoropolymer synthesis with alternating sequence regulation using a novel fluorinated xanthate agent via a light-driven process, which achieved on-demand copolymerization of chlorotrifluoroethylene and vinyl esters/amides under both batch and flow conditions at ambient pressure. This method creates a facile access to fluoropolymers with a broad fraction range of alternating units, low dispersities and high chain-end fidelity. Moreover, a two-step photo-flow platform was established to streamline the in-situ chain-extension toward unprecedented block copolymers continuously from fluoroethylene. Influences of structural control were illustrated with thermal and surface properties. We anticipate that this work will promote advanced material engineering with customized fluoropolymers.

Automated summary

This study achieved controlled synthesis of fluoropolymers for the first time using a novel fluorinated xanthate agent through a light-driven process. The alternating copolymerization of chlorotrifluoroethylene and vinyl esters/amides was successfully carried out under both batch and flow conditions. A two-step photo-flow platform was established to enable in-situ chain-extension for the continuous synthesis of advanced block copolymers from fluoroethylene.