Grafting PMMA onto P(VDF-TrFE) by CF Activation via a Cu(0) Mediated Controlled Radical Polymerization Process.

In the present work, poly(methyl methacrylate) (PMMA) is successfully grafted onto poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) side chains via directly activated CF bonds using Cu(0)/2,2'-bipyridine as catalyst. The reaction mechanism and the initiating sites can be confirmed by the structure of the graft copolymer. The graft copolymerization exhibits first-order kinetics, and reaction conditions can affect the chemical composition of the graft copolymer, including reaction time, reaction temperature, solvents, the amount of catalyst, and monomer. The introduction of rigid PMMA side chains onto P(VDF-TrFE) can effectively tune the displacement-electric field hysteresis behaviors of P(VDF-TrFE) from normal ferroelectric to anti-ferroelectric, even linear-like dielectric, under high electric field, resulting in dramatically reduced energy loss while maintaining the discharged energy density. This work may provide an effective strategy to introduce functional groups into P(VDF-TrFE) copolymer via activation of CF bonds.