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

Abstract

Several strategies to synthesize fluorinated (co)polymers containing phosphorous groups and their applications are reviewed. First, original fluoromonomers bearing phosphorous atoms are supplied from relevant routes. They may possess fluorinated atoms linked to the ethylenic carbon atoms with different structures, such as F2C=CF- or H2C=C(CF3)- and a phosphonated \uf077-function adjacent to an aliphatic or aromatic linker, while other monomers display a difluoromethylene dialkylphosphonate end group such as -CF2-P(O)(OR)2. Then, fluorinated copolymers were obtained according to various pathways: (i) by radical homopolymerization of monomers containing both fluorine and phosphorous atoms, (ii) by direct radical copolymerization of fluoromonomers and phosphorous-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 atoms) 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 phosphorous 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, biomedical properties from phosphorous ones), synergetic characteristics have been targeted. These properties allow such fluoro-phosphorous (co)polymers to be used as novel materials involved in various applications as polymer exchange membranes for fuel cells, self-etching adhesives for dental materials, adhesion promoters, flame-retardants, polymer blends, and anticorrosive coatings.