Ring-Opening Polymerization of Cyclic Hemiacetal Esters for the Preparation of Hydrolytically and Thermally Degradable Polymer

Polymers that are biodegradable in natural environments are desirable components of next generation sustainable materials. To date, polylactide is the most successful industrially compostable polyester available at only a small premium relative to polystyrene. Biodegradation of polyesters under industrial composting conditions proceeds via hydrolysis, followed by mineralization of polylactide oligomers to carbon dioxide, water, and humus. Hydrolysis of polylactide precedes mineralization and thereby presents the rate-limiting step in this process. The work in this thesis is motivated by the need to further tailor hydrolytic degradation profiles of sustainable polymers to allow for their degradation in a variety of natural environments. In this work we demonstrate the synthesis of novel cyclic hemiacetal ester monomers that are transformed to hydrolytically and thermally degradable polyhemiacetal esters. A thorough discussion of the polymerization mechanism under Lewis- and Bronsted acid catalysis was attained in this process to aid the scientific community in using these molecules most efficiently.