Synthesis and Characterization of Novel Materials from Underutilized Biomass Feedstocks

This dissertation investigates the synthesis and characterization of new bioderived polymers from a variety of different biomass sources. In one thrust, a series of new monomers and polymers are synthesized from a toxic and inedible chemical called amygdalin, which is naturally present in a wide range of stone fruit pits. This molecule was functionalized into a methacrylate derivative and converted to a series of polymers with varying chirality incorporation. By varying the stereochemistry of the monomer feedstock, a range of stereoregular polymers were produced that allowed for the examination of the effects that polymeric stereochemistry can have on the thermal properties and microstructure of a material. Exhaustive characterization on each of these materials was performed, and their ability to stereocomplex with each other was also explored. Concurrent with the fruit pit derived polymers, another series of polymers were planned that were derived from the sugar derived isosorbide. These polymers were intended to be utilized as another set of new materials that explored the effects of polymeric stereochemistry. Initial studies demonstrated the ability to successfully create this new material, but the focus of this project was shifted when a publication was released that displayed new avenues for the chain growth polymerization of the sorbitol derivative. The production of new monomers for this project was easily accomplished by modification of existing procedures, but ultimately proved unsuccessful in their ability to produce polymer through ring-opening metathesis polymerization (ROMP). A final aim of this material was the design of a specialty crosslinking agent that could be utilized as a bioderived additive for existing polymers, but this material ultimately proved too chemically unstable, and its rapid decomposition caused too many issues to continue. The final investigation into novel bioderived polymers utilized the primary component of pine sap, a terpene named α-pinene, to make new polymers. While α-pinene is not able to undergo ROMP itself, a facile synthesis proved capable of producing isomeric δ-pinene which possessed superb qualities for ROMP. This monomer demonstrably reached high conversions under ambient conditions to afford polymers with high molar mass, low dispersity, regioregularity, and stereoregularity. Furthermore, this monomer proved to be robust in nature and could tolerate appreciable quantities of impurities such as byproduct α-pinene, and could produce polymers with precise microstructures, even in the absence of solvent.