Direct Synthesis of Vinylidene Fluoride-Based Amphiphilic Diblock Copolymers by RAFT/MADIX Polymerization

We herein report the synthesis of original vinylidene fluoride (VDF)-based amphiphilic block copolymers by RAFT/MADIX polymerization. The controlled polymerization of VDF could be successfully mediated by a xanthate chain transfer agent as evidenced by size exclusion chromatography (SEC), ¹⁹F NMR, and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis. Copolymers of VDF and perfluoro(methyl vinyl ether) (PMVE) of varying controlled chain lengths were also obtained. Finally, the direct synthesis of main-chain fluorinated amphiphilic block copolymers was performed from hydrophilic poly(N,N-dimethylacrylamide) macro-RAFT agents. It is expected that this finding will open interesting perspectives for the development of new class of polymeric surfactants for the stabilization of emulsions based on water and supercritical carbon dioxide media.