Use of fluorinated organic compounds in living radical polymerizations

Controlled/ living radical polymerization (LRP) is a field of special interest because it allows tailoring well- defined macromolecular architectures such as telechelic, block, graft or star copolymers. Since the eighties, several techniques have been reported [such as the iniferter method, nitroxide- mediated radical polymerization (NMP), atom transfer radical polymerization (ATRP), iodine transfer polymerization (ITP), and reversible addition- fragmentation chain transfer (RAFT)] giving rise to a huge number of publications and patents. This review aims at illustrating the contribution of fluorinated organic compounds in this area of research through the use of fluorinated initiators (dithiocarbamates, xanthates, tetraphenylethanes, alkoxyamines, fluorinated alkyl halides, and dithioesters) or other fluorinated molecules (ligands, solvents). Another point depicts the LRP of various fluorinated monomers (methacrylates, acrylates, styrenics, and alkenes). Finally, fluorinated block and graft copolymers prepared by LRP have been reported. A review with 165 references.