Surfactant-free emulsion polymerization of vinylidene fluoride mediated by RAFT/MADIX reactive poly(ethylene glycol) polymer chains

A robust and straightforward synthesis of surfactant-free poly(vinylidene fluoride) (PVDF) latexes is presented using RAFT/MADIX-mediated emulsion polymerization. VDF emulsion polymerizations were conducted in the presence of commercial poly(ethylene glycol) chains (PEG-OH) and in the presence of the same chains carrying a dithiocarbonate (xanthate) chain end (PEG-X). The identification of the stabilization mode in both cases is carefully examined, considering the irreversible chain transfer reactions well known in VDF free radical polymerization. The particle size is significantly smaller when PEG-X was used, demonstrating the positive effect on particle stabilization of the involvement of xanthate chain end in the free radical process.