Beta-Irradiation of pure 1-alkyl-3-methylimidazolium-based ionic liquids

Abstract

1-Alkyl-3-methylimidazolium ionic liquids are common cellulose solvents and biomass pretreatment agents, while beta-irradiation (“e-beaming”) is often used to decrease the recalcitrance of biomass towards hydrolysis or saccharification. Aiming at the general goal of elucidating the interaction between lignocellulosics, imidazolium-based ionic liquids, and beta-irradiation, we studied the effect of beta-irradiation on the pure ILs 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium, both as chloride and acetate. Contrary to the expectation of inertness, irradiation caused degradation of the ILs, which was proportional to irradiation dosage, i.e., to irradiation time and intensity. At a dosage of 2400 kGy, 0.2% (2000 ppm) of the IL were chemically altered. The main degradation pathway is the formation of imidazole and N-methylimidazole with concomitant dealkylation. The cleaved-off alkyl groups, apparently in cationic form, react with the anions present, accounting for the formation of alkyl chlorides and alkyl acetates from the chloride ILs and acetate ILs, respectively. A second, minor pathway comprises the degradation of the imidazole ring under conversion of the C2-unit from the former C4-C5 moiety into ethylenediamine and reaction of the C1-unit from the former C2 with the IL anions. Because of the non-neglible byproduct formation, the degradation of the ILs upon beta-irradiation and possible side reactions of the resulting byproducts need to be kept in mind for all setups that involve beta-irradiation and imidazolium ILs simultaneously.Graphical abstract