Radical Cascade-Triggered Controlled Ring-Opening Polymerization of Macrocyclic Monomers

A strategy for the controlled radical ring-opening polymerization of macrocyclic monomers is reported. Key to this approach is an allyl alkylsulfone-based ring-opening trigger that can undergo a radical cascade reaction to extrude sulfur dioxide and generate an alkyl radical for controlled chain propagation. A systematic study correlating reaction conditions with polymer molecular weight and molecular weight distribution allowed excellent control over polymerization. The versatility of this radical cascade-triggered ring-opening polymerization approach was further demonstrated through the first radical block copolymerization of macrocyclic monomers, and the incorporation of degradable functionality into the polymer backbone.