pH-responsive non-surface-active/surface-active transition of weakly ionic amphiphilic diblock copolymers

The weakly ionic amphiphilic diblock copolymer polystyrene-b-poly(acrylic acid) was synthesized by nitroxy radical-mediated living radical polymerization with precise control of block length, block ratio, and polydispersity. Systematical surface tension experiments and foam formation observations revealed that this polymer was non-surface active under neutral and alkaline (pH 10) conditions, while it was surface active under an acidic condition (pH 3). This result supports our proposed origin of non-surface activity; the image charge repulsion at the air/water interface is essential in addition to very stable micelle formation in the bulk solution. At a higher pH (pH 12), the polymer showed slight surface activity since the added NaOH played a role as an added salt. The critical micelle concentration (cmc) was estimated by static light scattering. Cmc increased with increasing added salt (NaCl) concentration as was observed for other strongly ionic non-surface-active polymers. Hence, this trend is characteristic for non-surface-active polymers. The pH dependence of cmc was minimum at pH 8–10. Since the acrylic acid block is fully ionized under this condition, the strong image charge repulsion at this condition accelerated micelle formation at a low polymer concentration, which consequently decreased cmc. Micelles in bulk solution were confirmed by dynamic light scattering, and the salt concentration and pH dependencies of the hydrodynamic radius of the micelles were also estimated. The pH-responsive non-surface-active/surface-active transition observed in this study strongly supports the fact that the image charge repulsion is an essential factor for non-surface activity in addition to stable micelle formation in solution.