Imidazolium-based protic ionic liquids with perfluorinated anions: Influence of chemical structure on thermal properties

The influence of the cation chemical structure, namely its side chain, on the thermal properties of imidazolium-based protic ionic liquids (PILs) with different perfluorinated anions (trifluoromethanesulfonimide (TFSI), trifluoromethanesulfonic (TFS), and trifluoroacetic (TFA) acids) was studied. With that purpose, twenty-one PILs with various alkyl (methyl-, ethyl-, butyl- and vinyl-) and fluorinated (-CH2CF3, -CH2CHF2, and -CH2CH2F) side chains were successfully synthesized. Special attention was paid to an optimization of their synthesis conditions. The structure of synthesized fluorinated and alkylsubstituted PILs was confirmed by means of nuclear magnetic resonance (NMR) analysis (1D: H-1, F-19, C-13 and 2D: H-1 - F-19 HOESY experiments) and Fourier transform infrared (FTIR) spectroscopy, while PILs thermal behavior was determined by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) in dynamic and isothermal modes. The correlation between the PILs chemical structure and their thermal stability was established. It has been found that an increase of the length of alkyl side chain (methyl- < vinyl- < ethyl- < butyl-) leads to a lower melting point temperature. Moreover, it is shown that an increase in the amount of fluorine atoms in the cation chemical structure (-CH2F < -CHF2 < -CF3 ) leads to a PIL with a higher crystallinity (a higher melting point temperature) and a lower thermal stability. Thus, the best performance in terms of the thermal stability was reached for monofluorinated- (-CH2F) and butyl-TFSI PILs in liquid state: 370 degrees C and 400 degrees C, respectively, while the lowest thermal stability was obtained for trifluorinated- (-CF3) and vinyl-TFA PILs in solid state: 145 degrees C and 129 degrees C, respectively. (C) 2021 Elsevier B.V. All rights reserved.

Automated summary

The thermal properties of imidazolium-based protic ionic liquids (PILs) with different perfluorinated anions were studied by synthesizing 21 PILs with various alkyl and fluorinated side chains. The results showed that an increase in the length of alkyl side chains led to a decrease in melting point temperature, while an increase in the amount of fluorine atoms in the cation chemical structure led to higher crystallinity and lower thermal stability. The best thermal stability was observed in monofluorinated- and butyl-TFSI PILs in liquid state, while the lowest thermal stability was found in trifluorinated- and vinyl-TFA PILs in solid state.