Synthesis and properties of new sulfonated poly(p-phenylene) derivatives for proton exchange membranes. I

Several high molecular weight poly(2,5-benzophenone) derivatives were synthesized by high yield nickel-catalyzed coupling polymerization of 2,5-dichloro-4′-substituted benzophenones. The monomers were prepared by Friedel–Crafts catalyzed reaction of 2,5-dichlorobenzoyl chloride and several aromatic compounds. The resulting polymers are organosoluble and show no evidence of crystallinity by differential scanning calorimetry (DSC). The temperatures of 5% weight loss of the polymers via dynamic thermogravimetric analysis in air were above 480 °C. Sulfonation of selected polymers utilizing concentrated or fuming sulfuric acid at room temperature introduced sulfonic acid moieties to the aromatic side group. Activated fluoro aryl groups were also used to generate pendent sulfonated functionalities. The sulfonated polymers were examined for ion exchange capacities, water absorption capacities and proton conductivities. The sulfonated polymers were not good film formers, but could be demonstrated to show high values of proton conductivity in the range of 0.06–0.11 S/cm when supported on glass fabrics or via polymer blending strategies.