Synthesis and micellar properties of surface-active ionic liquids: 1-Alkyl-3-methylimidazolium chlorides

Abstract

A series of surface-active ionic liquids, RMeImCl, has been synthesized by the reaction of purified 1-methylimidazole and 1-chloroalkanes, RCl, R = C 10 , C 12 , C 14 , and C 16, respectively. Adsorption and aggregation of these surfactants in water have been studied by surface tension measurement. Additionally, solution conductivity, electromotive force, fluorescence quenching of micelle-solubilized pyrene, and static light scattering have been employed to investigate micelle formation. The following changes resulted from an increase in the length of R: an increase of micelle aggregation number; a decrease of: minimum area/surfactant molecule at solution/air interface; critical micelle concentration, and degree of counter-ion dissociation. Theoretically-calculated aggregation numbers and those based on quenching of pyrene are in good agreement. Gibbs free energies of adsorption at solution/air interface, Δ G ads 0 , and micelle formation in water, Δ G mic 0 , were calculated, and compared to those of three surfactant series, alkylpyridinium chlorides, RPyCl, alkylbenzyldimethylammonium chlorides, RBzMe 2Cl, and benzyl(3-acylaminoethyl)dimethylammonium chlorides, R ′ AEtBzMe 2 Cl , respectively. Contributions to the above-mentioned Gibbs free energies from surfactant methylene groups (in the hydrophobic tail) and the head-group were calculated. For RMeImCl, the former energy is similar to that of other cationic surfactants. The corresponding free energy contribution of the head-group to Δ G mic 0 showed the following order: RPyCl ≈ RBzMe 2 Cl > RMeImCl > R ′ AEtBzMe 2 Cl . The head-groups of the first two surfactant series are more hydrophobic than the imidazolium ring of RMeImCl, this should favor their aggregation. Micellization of RMeImCl, however, is driven by a relatively strong hydrogen-bonding between the chloride ion and the hydrogens in the imidazolium ring, in particular the relatively acidic H2. This interaction more than compensates for the relative hydrophilic character of the diazolium ring. As indicated by the corresponding Δ G mic 0 , micellization of R ′ AEtBzMe 2 Cl is more favorable than that of RMeImCl because the CONH group of the former surfactant series forms hydrogen bonds to both the counter-ion and the neighboring molecules in the micelle.