Phosphorus-Containing Fluoropolymers: State of the Art and Applications.

Several strategies to synthesize fluorinated (co)polymers containing phosphorus groups and their applications are reviewed. First, original fluoromonomers bearing phosphorus atoms are supplied from relevant routes. They may possess fluorinated atoms linked to the ethylenic carbon atoms with different structures, such as FC═CF- or HC═C(CF)- and a phosphonated ω-function adjacent to an aliphatic or aromatic linker, while other monomers display a difluoromethylene dialkylphosphonate end group such as -CF-P(O)(OR). Then, fluorinated copolymers were obtained according to various pathways: (i) by radical homopolymerization of monomers containing both fluorine and phosphorus atoms, (ii) by direct radical copolymerization of fluoromonomers and phosphorus-based monomers, or (iii) by chemical modification of fluorinated copolymers with phosphorus-based reactants. Conventional radical and controlled (or reversible deactivation radical polymerization, RDRP) copolymerization have also been explored. As for the chemical change of halogenated polymers, either conventional organic reactions (e.g., Arbuzov reaction from a chlorine, iodine, or bromine atom) or radiation grafting with specific monomers led to graft copolymers composed of a fluorinated backbone and phosphonated grafts. This second part also details aliphatic and aromatic fluorophosphorous copolymers in which dialkylphosphonates or phosphonic acids are reported. Finally, since fluorine and phosphorus atoms bring complementary relevant properties (low refractive index and dielectric constants, chemical inertness, high electrochemical, soils, and heat resistances, electroattractivity from fluorine atoms and high acidity, complexation, anticorrosion, flame retardant, and biomedical properties from phosphorus ones), synergetic characteristics have been targeted. These properties allow such fluoro-phosphorus (co)polymers to be used as novel materials involved in various applications such as polymer exchange membranes for fuel cells, self-etching adhesives for dental materials, adhesion promoters, flame retardants, polymer blends, and anticorrosive coatings.