Two series of high molecular weight disulfonated poly(arylene ether sulfone) random copolymers were synthesized as proton exchange membranes for high-temperature water electrolyzers. These copolymers differ based on the position of the ether bonds on the aromatic rings. One series is comprised of fully para-substituted hydroquinone comonomer, and the other series incorporated 25 mol % of a meta-substituted comonomer resorcinol and 75 mol % hydroquinone. The influence of the substitution position on water uptake and electrochemical properties of the membranes were investigated and compared to that of the state-of-the-art membrane Nafion. The mechanical properties of the membranes were measured for the first time in fully hydrated conditions at ambient and elevated temperatures. Submerged in water, these hydrocarbon-based copolymers had moduli an order of magnitude higher than Nafion. Selected copolymers of each series showed dramatically increased proton conductivities at elevated temperature in fully hydrated conditions, while their H gas permeabilities were well controlled over a wide range of temperatures. These improved properties were attributed to the high glass transition temperatures of the disulfonated poly(arylene ether sulfone)s.

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