A series of poly(phenylene oxide) (PPO) polymers bearing phosphonic acid groups on the methyl group and on the phenyl ring are synthesized as membrane materials for fuel cell applications. These phosphonic acid-based PPO membranes exhibited high chemical resistance, dimensional stability, and good proton conductivity even under low humidity condition. Among the membranes, the one in which the phosphonic acid moiety is attached to the polymer main chain with CO(CH 2 ) 5 shows highest proton conductivity under overall conditions even though it has the lowest water uptake and IEC value. A well-defined separation of the hydrophilic and hydrophobic phases suggests the phosphonic acid groups to form proton conduction channels via interchain hydrogen bonding. A high storage modulus of the membranes in various temperature ranges indicates that the membranes are suitable for use under a high temperature and low humidity conditions.
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