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

• Published in: Journal of organic chemistry Vol. 86; no. 19; pp. 13481 - 13490
• Main Authors: Pellerite, Mark J, Lomeda, Jay R
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 01.10.2021; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; QUATERNARY AMMONIUM; CARBON-MONOXIDE; ELECTROCHEMICAL REDUCTION; IMIDAZOLIUM CATIONS; CHEMICAL-REACTIVITY; FUEL-CELLS; DEGRADATION; SYSTEMS; HYDROXIDE; ALKALINE STABILITY
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.1c01563

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.