Formation of Hybrid Wormlike Micelles upon Mixing Cetyl Trimethylammonium Bromide with Poly(methyl methacrylate-co-sodium styrene sulfonate) Copolymers in Aqueous Solution

The association of cetyltrimethylammonium bromide, CTAB, with a series of P(MMAx-co-SSNa) random copolymers of sodium styrene sulfonate (SSNa) with methyl methacrylate (MMA) was explored in aqueous solution as a function of the MMA molar content, x, of the copolymers. The polyelectrolyte/surfactant complexation in aqueous solution was verified through pyrene fluorescence probing. In addition, turbidimetry studies in dilute or more concentrated aqueous solutions elucidated the phase separation behavior of the P(MMAx-co-SSNa)/CTAB systems as a function of the copolymer composition x and the surfactant to polyelectrolyte mixing charge ratio. It is found that practically phase separation is completely suppressed within the studied mixing range when the MMA content of the copolymers is ∼30−40 mol %. For lower MMA contents the polyelectrolyte/surfactant complex separates out from water, while for higher x values the solubility limits of the copolymers in water are attained. For the intermediate MMA contents, viscoelastic systems are obtained in more concentrated polymer/surfactant solutions provided that the polyelectrolyte is fully complexed with the cationic surfactant (1H NMR results). Moreover, the 1H NMR studies indicate that hybrid P(MMAx-co-SSNa)/CTAB wormlike micelles are formed in water under these conditions. Finally, it is shown that addition of salt prevents syneresis problems and facilitates the rheological investigation.