Doctor of Philosophy (PhD)



Document Type



The forefront of this study explored polymerization, specifically thermally-initiated, free-radical frontal polymerization of (meth)acrylic acid monomers while the monomers acted as a hydrogen bond donor of a deep eutectic solvent. These frontal polymerizations were shown to exhibit unusual front velocities and, in some cases, lower front temperatures than the frontal polymerization of the neat monomers or systems containing inert analogs in the place of the hydrogen bond acceptor of these monomer-containing deep eutectic solvents. The frontal polymerization will occur with a range of initiator concentrations including ones that were too low for the pure monomer systems to sustain a front. Because of the unusual behavior of these frontal systems, an isothermal photopolymerization was performed using these acid-monomer systems.

The second half of this work focuses on the studying kinetics of photopolymerization of these monomer-containing deep eutectic solvents using real-time infrared spectroscopy. Analysis of this real-time reaction monitoring indicated increases in polymerization rate that span orders of magnitude when comparing the deep eutectic solvent polymerization to pure monomer polymerization. A significant increase in polymerization rate was also seen in systems that include a methyl ester derivative of the hydrogen bond donor monomer in a nonpolymerizable deep eutectic solvent. Because the increase in rate was present in systems in which the monomer is a component of the deep eutectic solvent as well as when the monomer is just within a deep eutectic solvent, it can be determined that in addition to increased solvent viscosity, both preorganization due to hydrogen bonding and the polarity of the deep eutectic solvent around the monomer play a role in the enhancement of the rate.



Committee Chair

Pojman, John