We studied addition effect of sodium tetraphenylborate (NaBPh4), an organic salt with multiple hydrophobic sites, on thermoresponsive behavior of aqueous methylcellulose (MC) solution. By means of simultaneous measurements of viscosity and light transmittance during heating, it was clarified that the concentration of added NaBPh4 determines which of gelation and phase separation occurs first. Aqueous MC solution without NaBPh4 formed gels below the phase separation temperature, and therefore the phase separation remained incomplete. With increasing the concentration of added NaBPh4, the gelation temperature monotonously increased, whereas the phase separation exhibited complicated behavior. The phase separation temperature in gel phase drastically increased by addition of small amount of NaBPh4 in similar fashion to the gelation temperature, although the phase separation in gel phase faded away when the concentration of NaBPh4 exceeded ca. 0.05 M. Alternatively, liquid-liquid phase separation appeared. In contrast to the phase separation in gel phase, the liquid-liquid phase separation occurred essentially below the gelation temperature and proceeded completely to form macroscopic binary domains. Temperature of the liquid-liquid phase separation decreased initially, but it turned upward when the concentration of added NaBPh4 exceeded ca. 0.15 M and increased drastically with the further addition. In other words, the addition effect of NaBPh4 to the liquid-liquid phase separation switched from salting-out to salting-in. The liquid-liquid phase separation in progress was immobilized by application of additional heating above the gelation temperature. These various structure developments depending on the concentration of added NaBPh4 were observed by optical microscopy (OM) and small-angle light scattering (SALS). On the basis of the experimental results, we proposed a mechanism of the addition effects of organic anion with multiple hydrophobic sites on the gelation and the phase separation of aqueous MC.
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