Macromolecular Engineering and Depolymerization by Reversible Deactivation Radical Polymerization

Reversible deactivation radical polymerization (RDRP) techniques have significantly improved the synthetic feasibility of precise polymer synthesis. Polymers with well-defined molecular weight, molecular weight distributions, chain-end functionalities, and topologies can be prepared by RDRP. RDRP methods can be mediated by reversible halogen atom transfer in an atom transfer radical polymerization (ATRP), by degenerative transfer of a chain transfer agent (CTA) in a radical addition-fragmentation transfer polymerization (RAFT) polymerization, and reversible combination of a chain-end radical and a nitroxide and decomposition of the alkoxyamine in a nitroxide mediated polymerization (NMP). The thermodynamics of polymerization dictate whether the RDRP mechanism could be used to polymerize monomers into polymers, or if it is more favorable for polymers to depolymerize to monomers. The work presented in this thesis utilizes principles of all three methods to prepare and degrade polymers with complex topology.