Association and structure formation in oppositely charged polyelectrolyte–surfactant mixtures

Investigations dealing with association behaviour and structure formation in oppositely charged polyelectrolyte–surfactant mixtures in aqueous solutions are reviewed. Discussion is limited to a selection of vinyl based anionic polyelectrolytes that, when completely ionized, posses the same structural value of the linear charge density parameter. Particular emphasis is placed on the role of polymer chain properties in aggregates with surfactants. Chain characteristics are varied by changing the nature of the charged group, its ionization degree — when possible, the spatial distribution of these groups along the chain, i.e. the tacticity, and the hydrophobic character of other substituents attached to the chain. Quantitative information on the degree of binding in the form of binding isotherms is obtained using surfactant-sensitive membrane electrodes and microstructures of polyelectrolyte–surfactant complexes are determined by synchrotron small angle X-ray scattering. Considerable differences in the degree of binding (including the critical association concentration, CAC, values) and in structures are found. It is concluded that strong interactions in these systems arise from the electrostatic attraction, but this only forms the basis for initial extensive accumulation (anchoring) of surfactant ions in the vicinity of the polyion chain. When this is accomplished, additional specific interactions and effects may come into play. The most powerful of these interactions, the hydrophobic association between the chain and the micelle core, were found in polystyrenesulfonate, PSS, solutions. Other properties are less influential but still lead to CAC values that differ by more than one order of magnitude. These differences are explained by taking into account the chain conformation, flexibility, and hydrophobic character. Specific interactions between PSS and cetylpyridinium, CP, cations result in a soluble non-stoichiometric PSS–CP complex that could be characterized by measuring various solution properties as a function of polymer concentration and degree of complexation. The review is supplemented by including studies of complexation between the spherical fullerene hexamalonate anion and cationic surfactants, which demonstrate a high association tendency with characteristics similar to those found in binding of surfactants by linear polyelectrolytes.