Biodiesel: A green polymerization solvent

A number of polymer products are traditionally made using a solution polymerization technique. However, with increased environmental awareness and thus, concerns over the volatile organic content (VOC) associated with various polymer processes, there is an ongoing effort to find alternatives to traditional solvents.;In the first part of this study, solution polymerizations of four commercially important monomers (i.e., methyl methacrylate (MMA), styrene, butyl acrylate (BA) and vinyl acetate (VAc)) were studied at 60°C using FAME produced from canola oil as a solvent. Reactions were carried out at different solvent concentrations to verify the effect of the FAME on the polymerizations. Chain transfer to solvent rate parameters were obtained using the Mayo method. In addition, the effect of solvent on solution polymerizations of each monomer was investigated. This was suspected to contribute to a change in the lumped kinetic parameter (kp/kt1/2). The collected kinetic experimental data were modeled using a polymerization simulator.;In the second part of this thesis, canola-based FAME was used as a high boiling solvent in the solution polymerization of the aforementioned monomers at 120°C. Chain transfer to solvent rate constants were calculated and were employed in a polymerization simulator to predict the polymerization rates and the cumulative average molecular weights of the polymer product. As in the study at 60°C, changes in the lumped kinetic parameter with solvent concentration were incorporated into the free radical polymerization simulator; these changes considerably improved the model predictions.;In the third part of the thesis, the effect of FAME produced from different oil feedstocks on polymerization kinetics was investigated for styrene homopolymerizations at 60°C. Soybean oil, and 50% yellow grease-50% canola oil were the feedstocks employed in this study. Experimental results were compared to the runs using canola-based FAME at 60°C. Chain transfer to solvent constants were estimated for each solvent using the Mayo method and no significant difference between the values obtained from polymerization in different FAME was found. On the other hand, dissimilar effects on the rate of polymerization were observed. These were shown to relate to the degree of unsaturation of each FAME type. Model predictions of reaction rates and molecular weights for the investigated systems are also presented.;In an effort to use cleaner technologies, fatty acid methyl ester (FAME) was used for the first time as a polymerization solvent. Biodiesel or FAME has garnered much attention in recent years as an alternative to diesel fuel. It is environmentally benign and has a low volatility. Because biodiesel is a high boiling solvent, its use can increase productivity by enabling polymerizations at elevated temperatures. This would result in faster reaction rates and thus, shorter reaction times.