Photoiniferter Synthesis of Cyclic Polymers from Vinyl Monomers

Cyclic polymers synthesized from vinyl monomers are somewhat rare in the chemical literature. Examples published to date often involve harsh reaction conditions and lack versatility toward the vinyl monomer type. Reported here is a photoiniferter approach to synthesize cyclic polymers from vinyl monomers using mild reaction conditions (e.g., reactions conducted at room temperature with visible light irradiation). The synthetic process is simple and scalable and will enable the study of cyclic polymer properties on substantial amounts of material in the future. Evidence that the cyclic topology was achieved with little linear polymer contamination includes enhanced glass transition temperatures compared to linear polymers of similar molar mass as well as matrix-assisted laser desorption/ionization time-of-flight mass spectrometry results, confirming the target macromolecular structure.