The influence of pressure on the lower critical solution temperature miscibility behavior of aqueous solutions of poly(vinyl methyl ether) and the relation to the compositional curvature of the volume of mixing.

In mixtures of PVME and water, the influence of pressure on the LCST miscibility gap is determined covering the whole composition range and pressures from atmospheric pressure up to 900 MPa. The cloud point curve at atmospheric pressure has the characteristic bimodal shape in agreement with literature data. Upon increasing pressure the cloud point curve at the low concentration side decreases with pressure, whereas at the high concentrations the cloud point curve increases with pressure. The overall influence of pressure results in a less pronounced bimodality and ultimately the bimodal shape disappears. In addition to the pressure dependence of the miscibility behavior, the density of mixtures of water and PVME are determined at atmospheric pressure. The experimental excess specific volumes are negative for all measured compositions, but the compositional curvature varies with composition. The curvature of the excess specific volume is positive for the higher concentrations but it is negative in the lower composition range. The density measurements are linked to the pressure dependence of the LCST miscibility behavior using exact thermodynamic relationships. The excess specific volume and miscibility results are shown to be in good agreement. Moreover, it is shown that the Clapeyron equation, which is exact for pure components and also frequently assumed to apply to mixtures, is not valid in the system PVME/water. The system PVME/water is an example where the usual approximation of one-to-one correspondence between curvature and excess volume does not apply. Finally, the molecular origins for the observed excess volume and miscibility behavior are briefly discussed from theoretical and molecular simulation points of view.