Controlled sulfonation of poly(arylene ether sulfone)s and poly(arylene ether ketone)s with different molecular structures for polymer electrolyte membranes

Poly(arylene ether sulfone) copolymers derived from 9,9-bis(4-hydroxyphenyl)fluorene, bisphenol S and 4,4-difluorodiphenylsulfone and poly(arylene ether ketone) copolymers derived from 4-phenoxybiphenyl, diphenyl ether and isophthaloyl chloride were prepared as precursor polymers for sulfonation reaction in which sulfonic groups are introduced quantitatively into specified positions. Sulfonation reaction for these two series of copolymers by concentrated sulfuric acid was successfully carried out to give sulfonated polymers with controlled positions and degree of sulfonation. Thermal stability, moisture absorption and proton conductivity for these two series of copolymers were measured and the results were compared to those of perfluorosulfonic acid polymers.