Aggregation behavior of anionic surface active ionic liquids with double hydrocarbon chains in aqueous solution: Experimental and theoretical investigations

Two structurally similar imidazolium-based anionic surface active ionic liquids (SAILs) with double hydrocarbon chains, viz. 1-butyl-3-methylimidazolium bis(2-ethylhexyl) sulfosuccinate (C4mim-AOT) and 1-butyl-3-methylimidazolium bis(2-ethylhexyl) phosphate (C4mim-DEHP), were synthesized by a straightforward ion-exchange technique. A comparative investigation of their aggregation behavior with the corresponding traditional anionic surfactants, sodium bis(2-ethylhexyl) sulfosuccinate (Na-AOT) and sodium bis(2-ethylhexyl) phosphate (Na-DEHP) in aqueous solution was performed in detail by surface tension, electric conductivity, fluorescence spectra and dynamic light scattering measurements. The critical micelle concentration (CMC) values for the surfactants with double hydrocarbon chains obtained by different techniques are in good agreement. The surface activity of C4mim-AOT and C4mim-DEHP is superior to that of the corresponding traditional anionic surfactants, Na-AOT and Na-DEHP. It is also found that for anionic SAILs the nature of the anionic active group is a dominant factor in the determination of their aggregation behavior in aqueous solution, e.g. CMC and aggregation number, while the introduced organic cation plays a minor role. Theoretical calculations show that more conformations and electronegativity for DEHP anion leads to higher aggregation number and CMC values for C4mim-DEHP. This work is expected to be of practical values for the environmental friendly anion SAILs in nanomaterial synthesis and phase separation, etc.