Aqueous Block Copolymer−Surfactant Mixtures and Their Ability in Solubilizing Chlorinated Organic Compounds. A Thermodynamic and SANS Study

Within the topic of surfactant enhanced solubilization of additives sparingly soluble in water, volumetric, solubility, conductivity, and small-angle neutron scattering (SANS) experiments on mixtures composed of α,ω-dichloroalkane, surfactant, copolymer, and water were carried out at 298 K. The triblock copolymers (ethylene oxide)₁₃₂(propylene oxide)₅₀(ethylene oxide)₁₃₂ (F108) and (ethylene oxide)₇₆(propylene oxide)₂₉(ethylene oxide)₇₆ (F68) were chosen to investigate the role of the molecular weight keeping constant the hydrophilic/hydrophobic ratio. The selected surfactants are sodium decanoate (NaDec) and decyltrimethylammonium bromide (DeTAB) with comparable hydrophobicity and different charged heads. The α,ω-dichloroalkanes were chosen as contaminant prototypes. For the water + surfactant + copolymer mixtures, both the volume and the SANS results straightforwardly evidenced that (1) monomers of NaDec and copolymer unimers generate small mixed aggregates, (2) monomers of DeTAB combined with copolymer unimers do not form aggregates, and (3) unimeric copolymer is solubilized into NaDec and DeTAB micelles. The α,ω-dichloroalkanes presence induces the F108 aggregation even at very low copolymer composition. The addition of surfactant disintegrates the F108 aggregates and, consequently, the additive is expelled into the aqueous phase. Once F108 is in the unimeric state, it forms copolymer−micelle aggregates which incorporate the oil. In the case of F68 both the volumetric and the SANS data reveal that the additive does not alter the copolymer unimeric state. Moreover, they show that for the aqueous DeTAB−F68 system the additive trapping in both the copolymer−micelle aggregate and the pure micelles takes place being enhanced in the former aggregate in agreement with solubility experiments. For the NaDec−F68 mixtures, an additional solubilization process in the premicellar copolymer−surfactant microstructures occurs. SANS and conductivity data show that the additive incorporation into the mixed and the pure micelles does not essentially influence the structural properties of the aggregates.