Role of the alkyl fragment of initiating alkoxyamine in nitroxide mediated polymerization of styrene

The role of the alkyl fragment of alkoxyamine initiating the homopolymerization of styrene is experimentally and theoretically studied in the case of 2,2,6,6-tetramethylpiperidine-1-oxyl derivatives. The rate constants of homolysis and recombination are measured for the alkoxyamines under study. The characteristics of polymerization initiated by these compounds are experimentally examined. The kinetics of polymerization is theoretically calculated with allowance for the measured kinetic parameters and the experimentally detected side reaction of hydrogen-atom transfer to the nitroxide radical during the thermolysis of alkoxyamine 2-cyano-2-isopropyl-TEMPO.