Radical Ring-Crossover Polymerization of Macrocycles with Radically Exchangeable Dynamic Covalent Bonds

The authors report the synthesis and radical ring-crossover polymerization of macrocycles with radically exchangeable dynamic covalent bonds. The macrocyclic compounds with alkoxyamine units were designed and synthesized by condensation from alkoxyamine-based diol and the corresponding acid chlorides in the presence of pyridine under high-dilution condition. The macrocycles can thermally polymerize by intermolecular radical crossover reaction. Furthermore, the poly(alkoxyamine)s depolymerized to the monomers principally by the intramolecular radical exchange process under high-dilution conditions.