ABSTRACT
This chapter reviews developed molecular- thermodynamic theory of the complexation of nonionic polymers and surfactants in dilute aqueous solutions. The molecular model of complexation is based on the “necklace model”, in which a polymer-surfactant complex is described as composed of a series of spherical micelles with their surfaces covered by polymer segments and connected by polymer strands belonging to the same polymer molecule. The critical aggregation concentration is usually much smaller than the critical micelle concentration, which signals the onset of micelle formation in the corresponding polymer-free surfactant solution. A central finding of the theory is that polymer-surfactant complexation proceeds via a step-wise association process, namely, as the surfactant concentration is increased, complexes containing one micelle form first, and as long as this process continues the surfactant monomer concentration remains approximately constant. In order to actually predict the complexation behaviour, one needs to estimate the values of several molecular parameters associated with the surfactant head and the polymer.
