Mechanism-Based Invention of High-Speed Living Radical Polymerization Using Organotellurium Compounds and Azo-Initiators

Kinetic analysis reveals the existence of two competing pathways in the organotellurium-mediated living radical polymerization (TERP) at elevated temperature. The rate-determining step, namely, the thermal dissociation process, could be bypassed by the addition of conventional radical initiators, and the polymerization proceeded at low temperature by the degenerative transfer-mediated polymerization. The polymerization conditions are applicable to a variety of vinyl monomers, and the desired polymers form in a highly controlled manner.