Copoly(arylene ether nitrile) and Copoly(arylene ether sulfone) lonomers with Pendant Sulfobenzoyl Groups for Proton Conducting Fuel Cell Membranes

Three series of fully aromatic ionomers with naphthalene moieties and pendant sulfobenzoyl side chains were prepared via K2CO3 mediated nucleophilic aromatic substitution reactions. The first series consisted of poly(arylene ether)s prepared by polycondensations of 2,6-difluoro-2'-sulfobenzophenone (DFSBP) and 2,6-dihydroxynaphthalene or 2,7-dihydroxynaphthalene (2,7-DHN). In the second series, copoly(arylene ether nitrile)s with different ion-exchange capacities (IECs) were prepared by polycondensations of DFSBP, 2,6-difluorobenzonitrile (DFBN), and 2,7-DHN. In the third series, bis(4-fluorophenyl)sulfone was used instead of DFBN to prepare copoly(arylene ether sulfone)s. Thus, all the ionomers had sulfonic acid units placed in stable positions close to the electron withdrawing ketone link of the side chains. Mechanically strong proton-exchange membranes with IECs between 1.1 and 2.3 meq g(-1) were cast from dimethylsulfoxide solutions. High thermal stability was indicted by high degradation temperatures between 266 and 287 degrees C (1 degrees C min(-1) under air) and high glass transition temperatures between 245 and 306 degrees C, depending on the IEC. The copolymer membranes reached proton conductivities of 0.3 S cm(-1) under fully humidified conditions. At IECs above similar to 1.6 meg g(-1), the copolymer membranes reached higher proton conductivities than Nafion (R) in the range between -20 and 120 degrees C. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 734-745, 2011