Rate constants for the trapping of various carbon-centered radicals by nitroxides: Unimolecular initiators for living free radical polymerization

The recapping kinetics of a series of unimolecular initiators for free radi cal polymerization were investigated. The rate constants for the trapping o f various carbon-centered radicals were analyzed as a function of structura lly different nitroxides in order to determine suitable candidates for livi ng free radical polymerization (LFRP). The technique of laser flash photoly sis was used to determine the trapping rate constants for the radicals in t he presence of various amounts of nitroxide and to also gain insight into t he properties of the LFRP process.