Specific interactions of poly(4-vinyl phenol) gel with cationic and anionic surfactants

Binding behaviors of ionic surfactants (decyl- and dodecyltrimethylammonium bromide (C(10)TAB, C(12)TAB), sodium decane sulfonate (SDeSo), and sodium dodecyl sulfate (SDS)) to poly(4-vinyl phenol) (P4VPh) gel were investigated to elucidate a specific swelling behavior that has been found for P4VPh gel in aqueous solutions of tetraalkylammonium salts. With increasing cationic surfactant concentration, P4VPh gel significantly deswelled and then remarkably reswelled at a concentration somewhat below the respective cmc values. On the other hand, in the case of the anionic surfactants, the gel only showed a marked swelling at a concentration just below the respective cmc values. A similar charge-specific behavior of the surfactants was also found for the P4VPh dispersion system studied with a UV-vis spectroscopy; namely, in the cationic surfactant-P4VPh systems, the turbidity of the dispersion first increased with increasing the surfactant concentration and then decreased. This result suggests that aggregation of P4VPh particles first occurred and finally the particles were solubilized. A red shift followed by a blue shift observed for a pi-pi absorption of phenol at around 278 nm was also consistent with the aggregation-solubilization behavior. In the anionic surfactant-P4VPh system, however, only solubilization of the polymer particle was observed, and the UV peak only showed a blue shift. All these results in the gel and the dispersion systems strongly suggest that the cation-pi interaction is involved in the binding of the cationic surfactants to P4VPh.