Sulfonated Poly(aryl ether ketone)s Containing the Hexafluoroisopropylidene Diphenyl Moiety Prepared by Direct Copolymerization, as Proton Exchange Membranes for Fuel Cell Application

A series of sulfonated poly(aryl ether ketone) (SPAEK-6F) copolymers were prepared by aromatic nucleophilic polycondensation of hexafluoroisopropylidene diphenol with 5,5‘-carbonylbis(2-fluorobenzenesulfonate) and 4,4‘-difluorobenzophenone (DFBP) at various molar ratios. The synthesized SPAEK-6F polymers possessed high molecular weights revealed by their high viscosity, and tough and flexible membranes were obtained by casting from DMAc solution. The sulfonate or sulfonic acid content (SC) of the polymers, expressed as a number per repeat unit of polymer, was determined by 1H NMR spectroscopy and was in good agreement with the initial monomer ratios. The membranes exhibited increased water uptake and swelling with increasing SC and temperature. SPAEK-6F membranes with SC ranging from 0.6 to 1.14 maintained adequate mechanical strength after immersion in water at 80 °C for 24 h. Fenton's reagent test revealed that the SPAEK-6F membranes had good stability to oxidation. The proton conductivities of the SPAEK-6F films increased with SC and temperature, reaching values above 3 × 10-2 S/cm at 80 °C for SC ≥ 0.75. The tensile test indicated that the SPAEK-6F membranes with SC 0.75, 0.98, and 1.14 are tough and strong at ambient conditions. Consequently, these materials proved to be promising as proton exchange membranes and may be potentially useful for application in fuel cells operated at medium temperatures.