(Georgia Institute of Technology, 2022-07-25)
Smith, Ronald Aubrey
This thesis focuses on the development of a new thionolactone monomer class for radical ring-opening polymerizations (rROP). Typical monomers used in rROP have been marred with inactivity towards more activated vinyl monomers such as acrylates, acrylamides, and styrene. The thiocarbonyl platform discussed in this thesis uses the radicophilic nature of the thiocarbonyl to overcome these reactivity disparities. Project 1 focuses on the development of a first-generation thionolactone monomer which shows compatibility with more activated monomers (acrylates and acrylamides). Project 2 delves into a second-generation monomer which is also compatible with styrene in addition to acrylates and acrylamides. Project 2 further discusses applications for the blocky incorporation of this monomer in the form of degradable junctions. Project 3 focuses on derivatives of the second-generation monomer to tune rates of incorporation allowing for detailed block or gradient polymer microstructures. Project 4 explores thiophene derivatives of the first-generation monomer which facilitate homopolymerization and autopolymerization of these monomers.