Phase behavior of the carbon dioxide/toluene/poly(methyl methacrylate) ternary system

Carbon dioxide/organic polymer/solvent systems have several industrial applications, including supercritical polymerization. Various process parameters affect the phase behavior of these systems, thereby influencing the process design. Accordingly, the phase behavior of a carbon dioxide (CO₂)/toluene (Tol)/poly(methyl methacrylate) (PMMA) ternary system was investigated in this study. Measurements were performed using a synthetic method combined with laser displacement and turbidity measurement. Bubble points (vapor–liquid phase separation) were determined from changes in the piston displacement, whereas cloud points (liquid–liquid (LL) phase separation) were determined from changes in the turbidity The phase boundaries of CO₂ mass fractions ranging from 0.098 to 0.577 were measured by varying the Tol/PMMA ratio. The homogeneous phase area decreased when the ratio of PMMA to Tol increased, molecular weight of PMMA increased, and/or temperature decreased. These changes in the LL phase separation behavior were explained with reference to the free volume (v_f) and solubility parameter (δ) estimated using the Sanchez–Lacombe equation of state. The estimation of v_f and δ is expected to be helpful in comprehensively understanding the phase diagram and in predicting the phase behavior of CO₂/organic solvent/polymer systems.