Critical Insight into Mechanochemical and Thermal Degradation of Imidazolium-Based Ionic Liquids with Alkyl and Monomethoxypoly(ethylene glycol) Side Chains

Processes of mechanochemical degradation of imidazolium bis((trifluoromethyl)sulfonyl)imide ionic liquids with alkyl and monomethoxypoly(ethylene glycol) (mPEG) side groups were studied using the novel technique of mechanically stimulated gas emission spectroscopy. Mechanical stimulus caused degradation of both the anionic and cationic moieties. For the latter, the degradation was concentrated on the alkyl and ether chains rather than on the imidazole. For the anionic moiety, various degradation steps associated with the emission of CH x F y volatile products followed by SO 2 and SO 3 emission were identified. Simulation of frictional heat dissipation revealed that tribochemical reactivity was induced by the mechanical energy supply rather than the temperature increase. Thermal degradation of the same ionic liquids studied using thermogravimetric analysis and Fourier transform infrared spectroscopy was concentrated mainly on the cationic moiety. Thermal stability significantly depended on the side chains. The decomposition of mPEG-functionalized ionic liquids was a two-step process, where the lower temperature step corresponded to mPEG decomposition.