Effect of 2,2,6,6-tetramethyl-1-piperidinyloxy nitroxide substituent on kinetic parameters of pseudoliving polymerization

The main kinetic and thermodynamic parameters of the pseudoliving radical polymerization of styrene mediated by 4-linoleamido-2,2,6,6-tetramethyl-1-piperidinyloxy have been studied. It has been shown that the introduction of the said substituent into nitroxide leads to a marked reduction in the rate constant of reinitiation that is compensated for by the simultaneous reduction in the rate constant of reversible termination. As a result, the rate of pseudoliving polymerization, the rate of molecular mass growth, and the polydispersity of the polymer appear to be practically the same for processes mediated by both unsubstituted and substituted nitroxides.