Functional fluoropolymers for fuel cell membranes

Various routes to synthesise functional fluoropolymers used in membranes for fuel cell applications are presented. They can be separated into three main families of alternatives. The first concerns the direct radical copolymerisation of fluoroalkenes with fluorinated functional monomers. The latter are either fluorinated vinyl ethers, α,β,β-trifluorostyrenes or trifluorovinyl oxy-aromatic monomers bearing sulfonic or phosphonic acids. The resulting membranes are the well-known Nafion®, Flemion®, Hyflon®, Dow®, Aciplex® or BAM3G®. The second way deals with the chemical modification of hydrogenated polymers (e.g., polyparaphenylenes) with fluorinated sulfonic acid synthons. The third possibility concerns the synthesis of FP-g-poly(M) graft copolymers (where FP and M stand for fluoropolymer and monomer, respectively) obtained by activation (e.g., by irradiation with electrons, γ-rays or ozone) of fluoropolymers, followed by grafting of the monomers. The most used M is styrene, and a further step of sulfonation was achieved onto FP-g-PS, leading to FP-g-PS sulfonic acid graft copolymers.