Mechanism and kinetics of activation processes in a nitroxyl-mediated polymerization of styrene

A plausible method was developed to determine the frequency or rate constant of activation reactions. This was applied to a nitroxyl-mediated polymerization of styrene to establish the activation mechanism(s) of this system. A polystyrene-2,2,6,6-tetramethylpiperidinyl-1-oxy (PS-TEMPO) adduct was used as a `probe' polymer. The degenerative transfer may be neglected and the overall activation rate may be identified with dissociation at any other temperature unless the polymerization rate is increased too much by the addition of an initiator.