Comicellization of polystyrene-block-poly(ethylene oxide) with cationic and anionic surfactants in aqueous solutions:: Indications and limits

Interaction of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) with cationic and anionic surfactants was studied using light scattering, sedimentation in ultracentrifuge, and H-1 NMR. The complex structure of the mixed solution containing hybrid micelles, micellar clusters, and supermicellar aggregates was confirmed by independent experiments. By proton NMR, addition of anionic surfactant, sodium dodecyl sulfate (SDS), to PS-b-PEO solution results in loosening the micelle cores and an increase of the PS molecular mobility in the presence of surfactant. At the same time, incorporation of SDS into the block copolymer solution leads to noticeable broadening of the signals related to methylene protons of the surfactant, which can be assigned to a decrease of mobility of surfactant alkyl chains "immobilized" on the PS cores. These data along with ultracentrifugation of hybrid solutions containing PS-b-PEO and surfactant at various concentrations prove that comicellization occurs and mixed micelles are formed. However, this phenomenon is observed up to a certain limiting concentration of the surfactant. In the case of cetyl pyridinium chloride (CPC), increase of surfactant loading up to 0.05 mol/L results in the solutions containing CPC micelles along with hybrid micellar clusters and supermicellar aggregates.