Abstract

AbstractThe formation and the behaviour of radiation induced free radicals in poly[1‐(tert‐butoxy carbonylthio)ethylene] (2) and in a statistical copolymer 4 from O‐tert‐butyl S‐vinyl thiocarbonate (1) with N‐vinylpyrrolidone (1:1) was studied, using ESR spectroscopy. After γ‐irradiation at 77 K, tert‐butyl radicals and other species were detected in the polymers. The yield for the homopolymer was evaluated to be Gtert‐butyl = 0.18. Investigations on the behaviour of radicals with an annealing procedure revealed, that at first the tert‐butyl radicals disappear with increasing temperature and that a further warming up leads to a concentration rise of this radical species. A radical cation localized at the carboxy group is assumed as precursor of this reaction. Further reactions are discussed.

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