No abstract

The complex salt (ionic surfactant + polymeric counterion) cetyltrimethylammonium polyacrylate (CTAPA) has been synthesized, and its aqueous mixtures with cetyltrimethylammonium bromide (CTABr) have been studied. These mixtures differ from conventional oppositely charged polymer/surfactant mixtures in that the conventional counterion of the polyion (usually sodium, for the polyacrylate) is absent, which simplifies the studies and their interpretation considerably. The phase diagram of the CTAPA/CTABr/water system at >20 wt % water and at 40 °C has been established, representing the first truly ternary phase diagram of an oppositely charged polymer/surfactant pair in water. The two dimensions of the phase diagram may be chosen as the water content (in weight percent) and the fraction of bromide counterions, x Br (in units of charge equivalents). The phase diagram is characterized by a large hexagonal phase (at low water contents and for all values of x Br ), a small cubic phase (at 55 wt % water content and for x Br < 0.1), a narrow isotropic (micellar) phase (at high water contents and for x Br > 0.9), and a large multiphase region (at water contents >50 wt %) containing two or three of the cubic, hexagonal, or isotropic phases in coexistence. The cubic and hexagonal phases are connected to the corresponding phases that separate out from aqueous NaPA/CTABr mixtures. The maximum water uptake of the hexagonal phase is remarkably constant at ca. 50 wt % over a large CTAPA/CTABr composition range (x Br < 0.9). The study confirms previous conclusions that the polyacrylate counterions favor a higher aggregate curvature (leading to smaller aggregates) than do the bromide counterions.

Aqueous systems containing sodium polyacrylate (NaPA) and the surfactant cetyltrimethylammonium bromide (CTABr) can separate into a concentrated phase and a dilute phase. The phase separation can be induced by addition of water. Further addition of water causes the concentrated phase to become still more concentrated. A structural analysis of the concentrated phase shows that the surfactant ions (CTA+) are always aggregated into elongated micelles. These micelles are packed with short-range order (concentrated micellar phase) or long-range order (hexagonal phase). The ionic compositions of the concentrated and the dilute phase have been determined. They indicate that the association results from an ion-exchange process, where the polyacrylate ions displace some bromide counterions of the surfactant aggregates. The separation of a dilute aqueous phase and the deswelling of the concentrated phase are then explained by the gain in entropy of the simple salt (Na+ and Br-) that is released in the dilute phase.