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Initiation Mechanisms in Radical Polymerizations: Reaction of Cumyloxy Radicals with Methyl Methacrylate and Styrene
Rizzardo, Ezio,Serelis, Algirdas K.,Solomon, David H.
, p. 2013 - 2024 (2007/10/02)
Cumyloxy (1-methyl-1-phenylethoxy) radicals have been generated by thermolysis (60 deg C) of dicumyl hyponitrite in methyl methacrylate and styrene.The carbon-centred radicals formed by interaction of cumyloxyl with the respective monomers were trapped as stable adducts of 1,1,3,3-tetramethylisoindolin-2-yloxyl.Extensive hydrogen atom abstraction and methyl radical generation as well as double-bond addition were observed in methyl methacrylate.Styrene underwent only double-bond addition by both cumyloxy and methyl radicals.Some possible implications of these results for polymer structure are discussed.A kinetic study of the decomposition of dicumyl hyponitrite in cyclohexane at various temperatures gave k=7.7*1014exp(-13600/T) s-1 for the rate constant.Rate constants for the addition of cumyloxyl to methyl methacrylate (k ca.2*104 dm3mol-1s-1) and styrene (k ca. 2*105dm3mol-1s-1) at 60 deg C have been estimated
