CHAPTER 14: Use of Vinylidene Fluoride (VDF) Telomers to Obtain Well-architectured Fluoropolymers, and Their Applications

The radical telomerization of vinylidene fluoride (VDF) with different chain-transfer agents (CTAs) and the use of the resulting fluorinated telomers are described. First, although many studies have been reported on such a reaction, the most recent ones involving CCl₃Z, thiols, methanol, and alkanes will be summarized. Extension of the telomerization of VDF towards controlled radical polymerization [reversible deactivation radical polymerization (RDRP)] could be achieved using specific CTAs, such as 1-iodoperfluoroalkanes and xanthates. The second part of the chapter is devoted to well-designed architectures obtained from these VDF telomers (e.g. macromonomers, block, graft and star copolymers or dendrimers). These VDF telomers have been involved in several applications such as surface modifiers, non-perfluorinated surfactants, electroactive thin films, porous coordination polymers, hybrid fluorosilicones, and nanocomposites, and these applications are discussed. The interest in inserting VDF units lies in obtaining a hydrogenofluorinated chain that maintains satisfactory performance and is much less stable than perfluorinated chains produced from tetrafluoroethylene telomers for which bioaccumulation, toxicity, and persistence have been highlighted.