Determination of activation and deactivation rate constants of model compounds in atom transfer radical polymerization

The activation and deactivation rate constants in atom transfer radical polymerization (ATRP) were measured using model compounds. The activation rate constants were determined using HPLC or GC under the kinetic isolation condition achieved by trapping the generated radical with 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO). The deactivation rate constants were measured by trapping 1-phenylethyl radicals with TEMPO in a competitive reaction. The effects of several parameters in ATRP systems were examined, including alkyl groups, ligands, transferred groups, and solvents. The data obtained were consistent with ATRP kinetics and provided further quantitative insights into understanding the ATRP processes.