Genesis of the CSIRO polymer group and the discovery and significance of nitroxide-mediated living radical polymerization

The background to the formation of the Commonwealth Scientific and Industrial Research Organization (CSIRO) polymer group is discussed. In particular, the challenges of working with high-conversion polymerization, as found in commercial systems, and the need to explain variations in polymer properties led to important advances in the theory of radical polymerization and control over both the initiation and termination steps. Studies on the fate of the macro-monomer, formed in termination by disproportionation, led to an early form of addition/fragmentation now known as reversible addition-fragmentation chain transfer, whereas detailed studies on initiation pathways using nitroxide trapping led to nitroxide-mediated living radical polymerization. These studies contributed to the renaissance in free-radical polymerization studies. (c) 2005 Wiley Periodicals, Inc.