On the origins of nitroxide mediated polymerization (NMP) and reversible addition fragmentation chain transfer (RAFT)

The early experiments on radical polymerization, which were to lead to a study of nitroxide trapping of the initiation step and the interest in defect groups, particularly the macromonomers formed by termination by disproportionation, are discussed. Results from the nitroxide trapping clearly show that the initiation step ranges from simple clean addition to the head of the monomer, to complex addition/abstraction reactions. Careful selection of the monomer/initiation system is emphasized with particular reference to two common monomers, styrene and methyl methacrylate, and two initiating radicals, t-butoxy and benzoyloxy. The discovery of nitroxide mediated polymerization (NMP) from observations made during the nitroxide trapping work is reported and the ability to have a living radical system demonstrated with numerous examples. Similarly, the study of the copolymerization of macromonomers, formed by disproportionation of the propagating chains, is discussed with the discovery of β-scission and an early form of additionfragmentation reported. The evolution of reversible additionfragmentation chain transfer (RAFT) to a highly versatile and commercially attractive radical system is reported and the detailed chemistry behind the discovery of this living radical system discussed. Both NMP and RAFT enable the synthesis of structures not previously possible by radical polymerization and in some cases not possible by any other process.