Specific formation of hydrophobic aggregates of ionic thermoresponsive polymers with oppositely charged ionic surfactants under extremely dilute conditions

Abstract

Cationic and anionic thermoresponsive polymers were synthesized and the formation of their hydrophobic aggregates with ionic surfactants was studied at extremely low polymer concentrations. Alongside the hydrophobic interactions, electrostatic interactions between the ionic groups of the polymers and surfactants played a major role in the formation of the hydrophobic aggregates. In the absence of an ionic surfactant, extremely dilute (i.e., 0.01 wt %) polymer solutions did not become turbid, even when they were heated above the phase-transition temperature. However, above the phase-transition temperature, the polymer solutions became turbid upon the addition of a specific concentration of an ionic surfactant with the opposite charge. In contrast, no increase in the turbidity was observed when an ionic surfactant with the same charge was added to the solution, regardless of the concentration of the ionic surfactant. Even below the phase-transition temperature, the application of a fluorescent probe that responded to the hydrophobicity of its environment revealed that the ionic thermoresponsive polymers formed a hydrophobic environment with oppositely charged surfactants owing to the electrostatic and hydrophobic interactions, even though hydrophobic precipitates were not observed. Thus, the electrostatic interactions between polymers and surfactants played crucial roles in the formation of hydrophobic aggregates under extremely low concentration of the polymers as well as the hydrophobic interactions did.