Mechanistic Investigation of ?-Thiono-Caprolactone Radical Polymerization: An Interesting Tool to Insert Weak Bonds into Poly(vinyl esters)

The incorporation of heteroatoms into the backbone commodity polymers prepared by radical polymerization is an elegant way to confer (bio)degradability such materials. This could be achieved via ring-opening cyclic monomers. Thionolactones have recently been identified as promising comonomers for (rROP), but they react only with activated monomers acrylate and acrylamide derivatives. Herein, we describe two thionolactone monomers, oxepane-2-thione, i.e., ?-thiono-caprolactone (thCL), 7-butyloxepane-2-thione, ?-thiono-decalactone (thDL), capable performing less vinyl acetate (VAc) produce readily degradable copolymers insertion thioesters containing repeating units. A thorough mechanistic investigation was performed understand reactivity We initiation main parameter perform In a specific case, poly(?-thCL) homopolymer successfully obtained. Concerning copolymerization acetate, variety polymerizations differing feed ratios were performed, degradability aminolysis examined size exclusion chromatography (SEC). To demonstrate usefulness thionolactones, block thioester linkages involving N,N-dimethylacrylamide VAc also degraded.