Rpn. Veregin et al., THE ROLE OF THERMAL INITIATION IN NITROXIDE MEDIATED LIVING FREE-RADICAL POLYMERIZATIONS, Chemistry Letters, (5), 1997, pp. 467-468
The BPO initiated ''living'' polymerization of styrene in the presence
of nitroxide is not consistent with the recently proposed steady-stat
e mechanism, which requires constant nitroxide and polymer radical con
centrations, and equal initiation and termination rates. It is shown t
hat none of these conditions are met. The data is consistent with a po
lymerization rate that is dominated by nitroxide, not by the rates of
thermal initiation and termination. Further, the use of agents that re
duce thermal initiation shows that thermal initiation is not necessary
to ensure that the polymerization proceeds, nor to ensure fast rates.