Graduation Year


Document Type




Degree Granting Department

Chemical Engineering

Major Professor

Aydin K. Sunol, Ph.D.

Committee Member

John T. Wolan, Ph.D.

Committee Member

Vinay K. Gupta, Ph.D.


Polymers, Solubility, Methyl methacrylate, Poly (methyl methacrylate), Statistical associating fluid theory


Environmentally friendly processing of materials is becoming an increasingly important consideration in a wide variety of emerging technologies. Polymer processing, in particular, has benefited tremendously in this venue from numerous advances achieved using high-pressure carbon dioxide (CO2) as a viscosity modifier, plasticizing agent, foaming agent, and reaction medium. Polymer processing in supercritical fluids has been a major interest for a portfolio of materials processing applications including their impregnation into porous matrices. Also, SCF solvents are being examined as a media for polymerization processes, polymer purification and fractionation, and as environmentally preferable solvents for solution coatings. Pressurized CO2 is inexpensive, sustainable, relatively benign, and versatile due to its gas-like viscosity and liquid-like densities, which can be controllably tuned through appropriate choice of temperature and pressure. Addition of high-pressure CO2 to polymer systems can have a profound impact on their thermodynamic properties and phase behavior, since the number of interacting species increases due to the high-pressures, so that the compressibility also increases, as well as the plasticity effects. Even then, polymers are only sparingly soluble in CO2 unless one uses an entrainer or surfactant. An addition of a liquid monomer co-solvent results in greatly enhanced polymer solubility in the supercritical fluid at rather mild conditions of lower temperatures and reduced pressures. The focus of this research is to measure, evaluate and model the phase behavior of the methyl methacrylate-CO2 and the poly (methyl methacrylate)-CO2-methyl methacrylate system, where methyl methacrylate plays role of a co-solvent. Cloud-point data are measured in the temperature range of 30-80°C, pressures as high as 300 bar, co-solvent concentrations of 27 and 48.4 wt% MMA, and varying PMMA concentrations of 0.1, 0.2, 0.5, and 2.5 wt%. Solubility data is reported for these systems. The experimental results are modeled accurately using the Statistical Associating Fluid Theory (SAFT) for multicomponent polymer/solvent mixtures. The measured solubility data appears to be significantly different than previously published results by McHugh et al, Fluid Phase Equilibria, 1999. Thorough investigation, re-calibration of the equipment, and repetition of the measurements has proved that the measured data is entirely correct and the reference data is significantly off, which indirectly gives credit to this work and opens room for amendments of those results. In addition, a reasonably closer qualitative match is achieved with the SAFT model used in this work as opposed to the modeling results published by the McHugh group.