Correlation of thermodynamic modeling and molecular simulations for liquid–liquid equilibrium of ternary polymer mixtures based on a phenomenological scaling method

In our previous study [S.Y. Oh, Y.C. Bae, J. Phys. Chem. B 114 (2010) 8948–8953], we presented a new method to predict liquid–liquid equilibria in ternary simple liquid mixtures by using a combination of a thermodynamic model and molecular simulations. As a continuation of that effort, we extend our previously developed method to ternary polymer systems. In the simulations, we used the dummy atoms to calculate the pair interaction energy values between the polymer segments and the solvent molecules. Furthermore, a thermodynamic model scaling concept is introduced to consider the chain length dependence of the energy parameters. This method was applied to ternary mixtures incorporating low to high molecular weight polymers. The method presented here well described the experimental observations using one or no adjustable parameters.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► A novel approach to calculations of LLE of ternary polymer mixtures is introduced. ► We use a combination of a thermodynamic model and molecular simulations. ► A scaling on the energy values is employed for correlations. ► Good agreement was obtained using one or no adjustable parameters.