Characterizing Cation Chemistry for Anion Exchange Membranes-para-Alkyl-Substituted Benzyltetramethylimidazolium and Benzyltrimethylammonium Salts in Base.

Base stability and degradation of imidazolium-functional materials have been a focus of research on anion exchange membranes for electrochemical devices. Despite extensive work, mechanistic questions can cloud efforts to correlate results from model compounds and polymeric membranes. Here, we report an NMR study of behavior in aqueous KOH of benzyltetramethylimidazolium and benzyltrimethylammonium salts with and without para-alkyl-substitution to probe whether base attack at the alkyl substituent plays a role in the reaction pathways. In all cases, the major products from the imidazolium salts are consistent with hydrolytic ring fragmentation as the principal mode of decomposition. Also, relative decomposition kinetics for both types of salts provided no conclusive evidence for a change in reaction mechanism upon introduction of the alkyl substituent. While our data do not rule out base attack at the alkyl group in the cases where rate differences were noted, these differences appear to be better attributed to reaction medium effects of submicrometer oil phase droplets arising from salt aggregation.

Characterizing Cation Chemistry for Anion Exchange Membranes-A Product Study of Benzylimidazolium Salt Decompositions in the Base.

Imidazolium functionality has played a prominent role in research on anion exchange membranes for use in alkaline electrochemical devices. Base stability and degradation of these materials has been much studied, but in many instances, product pathways have not been thoroughly delineated. We report an NMR study of base-induced decomposition products from three benzylimidazolium salts bearing varying extents of methyl substitution on the imidazolium ring. The major products are consistent with a hydrolytic ring fragmentation pathway as the principal mode of decomposition. We observe several new products not previously reported in the literature on imidazolium salt degradation, including benzilic acid rearrangement products formally derived from intermediate 1,2-dicarbonyl compounds or their equivalents. However, the overall reactions are complex, the yields of observed products do not account for all consumed starting materials, and mechanistic ambiguities remain.