Poly Vinyl Ketones, A Tunable Class of Photodegradable Polymers

ABSTRACT

Photopolymerization and photodegradation are growing research fields, with new discoveries in efficient photocatalytic systems, better controlled polymerizations, and triggered release of particles through photodegradation. Many of the recent developments in photopolymerization and photodegradation have been enabled by recent developments in controlled polymerization, coupled with photochemistry. Although new developments in efficient photopolymerization have been ongoing, less focus is placed on expanding the focus and scope of monomers. Vinyl ketones have received significantly less attention than other vinyl monomers such as acrylates and styrenes. However, recent work has shown they are well suited for photochemistry, with the potential for mild photopolymerization under visible light, in the absence of catalysts, and efficient photodegradation when exposed to UV radiation.

Here the potential for controlled photopolymerization of vinyl ketones will be explored. The proposed mechanisms, based on Norrish chemistry intrinsic to the ketone group, for photopolymerization and photodegradation will be explored. The fundamental architecture of the poly(vinyl ketones) will be explored, with modulation of the molecular weight distribution, formation of block copolymers and the ability to selectively photodegrade the vinyl ketone segments. Block polymers and thermoplastic elastomer type materials based on these block polymers will be explored. Finally, modulation of polymers through UV induced photodegradation will be explored. The unique ability to respond differently to distinct wavelengths of light makes vinyl ketone polymers appealing for downstream photodegradation properties. Of particular interest are the impact of functional group on the photodegradation rates, polymerization rates and the product distribution after degradation. Finally the impact of photodegradation in self assembled nanoparticles will be highlighted as a mechanism to change the morphology.

BIOGRAPHY

Dominik Konkolewicz completed his Doctoral studies at the University of Sydney in 2011. Subsequently, he moved to Carnegie Mellon University, to commence his postdoctoral work (2011-2014). In 2014 he joined the Chemistry and Biochemistry Faculty at Miami University. Dominik was promoted to Associate Professor in 2019, Full Professor in 2022 and University Distinguished Professor in 2025. His group develops new polymeric materials for applications ranging from new photo responsive structures, materials that can repair themselves and adapt upon addition of fuels, bioconjugates, and polymeric systems for lipid self-assembly for membrane protein analysis. Recurring themes in his research are using physical chemistry principles to guide the development of new organic materials and the use of mechanistic analysis to guide sustainability and biomaterials applications. He has published over 180 peer reviewed articles over his career. In addition Dominik is involved in the Polymeric Materials Science and Engineering division of the American Chemical Society, where he currently serves as the Chair Elect.