Hydroxide anion conducting solid polymer membranes, also termed anion exchange membranes, are becoming important materials for electrochemical technology, and activity in this field, spurred by renewed interest in alkaline fuel cells, is experiencing a resurgence. Solid polymer anion exchange membranes enable alkaline electrochemistry in devices such as fuel cells and electrolyzers and serve as a counterpoint to proton exchange membranes, of which there is a large body of literature. For their seeming importance, the details of transport in alkaline exchange membranes has not been explored thoroughly. In this work, a chloromethylated polymer with a polysulfone backbone was synthesized. 1 H NMR spectroscopy was performed to determine the chloromethyl content and its position on the polymer structure. The chloromethylated polymer was solution cast to form clear, creasable films, and subsequent soaking of these films in aqueous trimethylamine gave benzyltrimethylammonium groups. The resulting anion exchange membranes swell in water and show varying degrees of ionic conductivity depending on their ion exchange capacity. The water mobility in the anion exchange membranes was greater than in previously studied proton exchange membranes; however, the transport properties in these new materials were lower than what might have been expected from the water behavior. This comparison gives some insight as to future anion exchange membrane design objectives.

Cationic polymer membranes that conduct free anions comprise an enabling area of research for alkaline membrane fuel cells and other solid-state electrochemical devices that operate at high pH. The synthesis of anion exchange membranes based on a poly(phenylene) backbone prepared by a Diels-Alder reaction is demonstrated. The poly(phenylene)s have benzylic methyl groups that are converted to bromomethyl groups by a radical reaction. Cationic polymers result from conversion of the bromomethyl groups to ionic moieties by quaternization with trimethylamine in the solid state. The conversion to benzyltrimethylammonium groups is incomplete as evidenced by the differences between the IEC values measured by titration and the theoretical IECs based on 1 H NMR measurements. The anion exchange membranes formed from these polymers have hydroxide ion conductivities as high as 50 mS/cm in liquid water, and they are stable under highly basic conditions at elevated temperatures.

Anion exchange membranes comprised of a poly(phenylene) backbone and one of five different cationic head‐groups are prepared, briefly characterized, and tested for stability in 4 M KOH at 90 °C. The two membranes with resonance‐stabilized cations (benzyl pentamethylguanidinium and benzyl N‐methylimidazolium) show large (>25%) decreases in both conductivity and ion exchange capacity (IEC) after just one day of testing. The membrane with benzyl trimethylammonium cations shows a 33% loss of conductivity (14% decrease in IEC) after 14 days while the membrane with trimethylammonium cations attached by a hexamethylene spacer shows the least degradation: a 5% loss of conductivity over 14 days with no accompanying loss in IEC. A similar membrane which has a six‐carbon spacer and a ketone adjacent to the phenyl ring shows much lower stability, suggesting that the ketone takes part in degradation reactions. © 2012 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1736–1742, 2013

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