The 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 …