Macromolecules · 1997 · 80 citations · 23 references
Natural SciencesChemistryOrganic ChemistryPolymer ChemistryPolymer EngineeringFree-radical PolymerizationOlefin PolymerizationPhotocatalysisPhotochemical SynthesisPolymerization ProcessesRadical ReactionsFree Radical OxidationLiving Radical PolymerizationNitroxide-mediated PolymerizationOxidative CatalysisRadical Trapping
Low-temperature methods for the preparation of monomeric initiators for use in “living” free radical olefin polymerizations have been developed. Oxidative methods for generating carbon radicals in the presence of nitroxide traps such as TEMPO utilize PbO 2 with benzylic, alkyl, or phenylhydrazines or CuCl 2 with lithium enolates. Photolytic methods employ [Cp(CO) 2 Fe] 2 with a benzylic bromide, diphenyl disulfide with styrene, or di- tert -butyl peroxide with ethers. The use of di- tert -butyl hyponitrite with ethers generates carbon radicals at 50 °C that are trapped by TEMPO.
23