Polymerization of methyl methacrylate in the presence of a nonpolar hydrocarbon solvent. I. Construction of a complete ternary phase diagram through an in situ polymerization

This article presents the ternary phase diagram for methyl methacrylate (MMA), poly(methyl methacrylate) (PMMA), and n-hexane system at 70°C. It was constructed by both theoretical calculations and online laser light scattering (LLS) technique. In situ polymerization of MMA in a nonpolar nonsolvent carried out in a LLS cell provides a new means for the accurate detection of the cloud points of highly viscous polymer mixtures, with polymer weight fractions over 0.6. The ternary phase diagram measured in this study can be used to design the reaction conditions for the precipitation and/or dispersion polymerization in a nonpolar nonsolvent medium where polymerization kinetics as well as polymer particle morphologies are strongly affected by thermodynamic phase separation phenomena.