Mean-field lattice equations of state: 5. Influence of pressure on liquid-liquid phase behaviour of polymer blends

Abstract

The semi-phenomenological (SP) treatment and a modified form of the mean-field lattice-gas (MFLG) model were used to investigate the influence of pressure on the phase behaviour of polymer blends. It was shown that the peculiar phase relations of the system poly(ethyl acrylate)/poly(vinylidene fluoride) could be reproduced in a qualitative way. Positive and negative signs for the excess volume could be predicted in accordance with the observed pressure-temperature-weight fraction relations. Furthermore the effect of pressure on the location of binodals for oligomeric mixtures of polybutadiene and polystyrene was represented quantitatively with the MFLG model and the SP treatment. It was shown that end group contributions cannot be neglected if polymers of low molar mass are involved. It was further demonstrated that the SP approach only requires one interaction function to represent all critical data whereas in the MFLG model different interaction terms, one for each system, are necessary in order to obtain good descriptions. Both descriptions are found to be superior to a modified version of the Flory equation of state theory.