Thermal decomposition behaviors of imidazolium-type ionic liquids studied by pyrolysis-gas chromatography.

Thermal decomposition behaviors of a series of imidazolium-type ionic liquid samples were studied by pyrolysis-gas chromatography at 550 degrees C using various detectors. As for the imidazolium halides, haloalkanes and 1-alkylimidazoles corresponding to the alkyl substituents were mainly formed through the nucleophilic attacks of halide ions to the alkyl groups followed by C-N bond cleavage, along with a minor amount of alkenes. Meanwhile, in the case of the ionic liquids with BF(4), PF(6) and CF(3)SO(3) anions, corresponding alkenes were predominantly produced along with 1-alkylimidazoles rather than haloalkanes. No boron-containing products were found even from the samples with BF(4) anion, whereas minor but clear peaks of phosphorous-containing products were observed in the pyrograms of the samples with PF(6) anions. As for the samples with longer alkyl group, the pyrolyzates reflecting the C-C bond scissions in the alkyl groups were also formed to some extent. Meanwhile, imidazole rings did not decompose under the experimental conditions at around 550 degrees C.