Synthesis of Fluoropolymers Using Borane-Mediated Control Radical Polymerization for Energy Storage Applications

This chapter discusses two closely relative areas, including the borane-mediated control radical polymerization to prepare some unique fluoropolymer structures and the resulting fluoropolymers for energy storage applications. The system of borane/oxygen control radical initiators is surprisingly effective for initiating polymerization of fluoromonomers, such as vinylidene fluoride (VDF), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), at ambient temperature. The control polymerization is characterized by predictable molecular weight, narrow molecular weight distribution, formation of chain end functionalized polymers and diblock copolymers, and tolerance to many functional groups that usually cause chain transfer reactions in regular free radical polymerization. The chapter focuses on the application of this stable borane initiator technology to prepare fluoropolymers having one or two terminal functional groups, which includes the published results in fluorinated acrylate and new observation in VDF-based polymers.