Effect of 1‐Butyl-3-methylimidazolium halide on the relative stability between sodium Dodecyl Sulfate Micelles and sodium Dodecyl Sulfate−Poly(ethylene oxide) Nanoaggregates

Abstract

It is well-known that ionic liquids (ILs) alter the properties of aqueous systems containing only surfactants. However, the effect of ILs on polymer–surfactant systems is still unknown. Here, the effect of 1-butyl-3-methylimidazolium bromide (bmimBr) and chloride (bmimCl) on the micellization of sodium dodecyl sulfate (SDS) and its interaction with poly(ethylene oxide) (PEO) was evaluated using conductimetry, fluorimetry, and isothermal titration calorimetry. The ILs decreased the critical micellar concentration (cmc) of the surfactant, stabilizing the SDS micelles. A second critical concentration (c2thc) was verified at high SDS concentrations, due to the micelle size decrease. The stability of PEO/SDS aggregates was also affected by ILs, and the critical aggregation concentration (cac) of SDS increased. Integral aggregation enthalpy changed from −0.72 in water to 2.16 kJ mol–1 in 4.00 mM bmimBr. IL anions did not affect the SDS micellization or the beginning of PEO/SDS aggregation. Nevertheless, when chloride was replaced with bromide, the amount of SDS bound to the polymer increased. At 100.0 mM IL, the PEO-SDS interaction vanished. We suggest that the effect of ILs comes from participating in the structure of the formed aggregates, interacting with the SDS monomers at the core/interface of the micelles, and promoting preferential solvation of the polymer.