Degradable vinyl polymers via radical ring-opening polymerization have become a promising solution to the widespread use of non-degradable vinyl plastics. However, achieving tunable and even distribution of labile functional groups in the backbone of degradable vinyl polymers remains challenging. Here, a general approach to the synthesis of degradable vinyl random copolymers via photocontrolled radical ring-opening cascade copolymerization (rROCCP) is developed. The rROCCP of macrocyclic allylic sulfones and acrylates or acrylamides mediated by visible light at ambient temperature achieved near-unity comonomer reactivity ratios over the entire range of the feed compositions. Such a powerful approach provides degradable vinyl random copolymers with comparable material properties to their non-degradable counterparts. Experimental and computational evidence also revealed an unusual reversible inhibition of chain propagation by in situ generated sulfur dioxide (SO2), which was successfully overcome by reducing the solubility of SO2 during polymerization.

Degradable vinyl random copolymers via photocontrolled radical ring-opening cascade copolymerization

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ACS Fall 2022

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