Abstract In this work, a strategy of C–F bond activation for grafting modification of poly(vinylidene fluoride‐trifluoroethylene) (h‐P(VDF‐TrFE), TrFE is dominantly as –CF2CH2–CFHCF2– sequence) using an Ir‐based photoredox catalyst is reported. The graft polymerization exhibits first‐order kinetics, and the chemical composition of the graft copolymer can be easily adjusted by changing the reaction conditions. Importantly, the side reaction of dehydrofluorination (β‐H elimination) can be effectively avoided, which occurs in the previously reported copper complex catalytic system. Moreover, the purification process is greatly simplified due to the extremely low content of catalyst added. This work may provide a facile strategy for incorporating functional groups into h‐P(VDF‐TrFE) via directly activating C–F bond under mild conditions.
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