Synthesis of proton-conductive Perfluoro(Benzylphosphonic Acid)s via polymer side chain phosphorylation

Nafion™ utilizes -SO₃H groups for proton conduction. Using an alternative proton-exchange functionality like -PO₃H₂, -COOH, etc., to replace -SO₃H in ion conductive fluoropolymers has attracted significant attention. For example, composite membranes comprising Nafion™ and perfluoro(carboxylic acid) bearing a -COOH group on its side chains have been used in color-alkali cells to reduce unwanted electrolyte crossovers. In the present paper, we reported a new synthetic strategy for constructing novel -PO₃H₂-bearing fluoropolymers (FBP). Our method employs a ZnI₂-promoted phosphorylation reaction of triethyl phosphite that converts benzyl alcohol on a side chain of a fluoropolymer into a benzylphosphodiester group, followed by trimethylsilyl chloride (TMSCl) hydrolysis to yield FBP. This strategy has enabled us to graft a fluoropolymer side chain directly with phosphonic acid. Although the in-plane proton conductivities of FBP fluoropolymers are lower than those of Nafion™ 115, most FBPs, especially Homo-FBP that has no fluoroalkyl ether group on its side chains, are significantly more stable against hydroxyl radical degradations in Fenton tests. This paper presents a new method for the synthesis of -PO₃H₂-containing fluoropolymers and our work also confirms a novel strategy for enhancing the long-term stability of a proton-conductive fluoropolymer in electrical devices—eliminating or reducing fluoroalkyl ether groups on the side chains of the polymer.