Facile Grafting Modification of Poly(Vinylidene Fluoride‐co‐Trifluoroethylene) Directly from Inner CHCH Bonds

Abstract To endow new functions to poly(vinylidene fluoride) (PVDF) based fluoropolymers and expand their application fields, chemical modification is a useful tool to achieve this goal. In this work, the grafting of varied vinyl monomers onto PVDF backbone is achieved via the radical polymerization process using poly(vinylidene fluoride‐ co ‐trifluoroethylene) bearing CHCH double bonds (P(VDF‐TrFE‐DB)) as initiator, which is obtained by a controlled dehydrofluorination reaction of P(VDF‐TrFE). The graft copolymerization is achieved under mild conditions, and the composition of the graft copolymers can be regulated by changing the reaction conditions. Moreover, the introduction of low‐polar poly(methyl methacrylate) (PMMA) side chains can effectively adjust the crystallization and dielectric properties of P(VDF‐TrFE). This work may offer a facile method for preparing PVDF‐based graft copolymers.