The formation and behaviour of radiation-induced free radicals in statistical copolymers of ethoxyvinylthiomethane (1a) with N-vinylpyrrolidone (2) (1:2,5) and of ethylthiovinylthiomethane (1b) with 2 (1:3,5) has been studied using electron spin resonance spectroscopy. After a γ-irradiation of the copolymers at 77K Cα-radicals in the vinylpyrrolidone moieties could be detected. Investigations on the behaviour of these radicals with an annealing procedure revealed that only in the copolymer (3b) with the dithioacetal group a transfer reaction of hydrogen atoms to the Cα-radicals in the vinylpyrrolidone moieties occurs. This process may be regarded as a repair mechanism. Es wurde die Bildung …

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 …

Formation and behaviour of radiation induced free radicals in statistical copolymers from vinyl hydrosulfide and styrene (1:1, 1:4, and 1:10) were investigated by means of ESR spectroscopy. The corresponding homopolymers were also included in these studies. After γ-irradiation of the copolymers at 77 K and subsequent annealing to 293 K it was possible to detect thio radicals. Their relative yields were found to increase with increasing styrene content. Investigations regarding the thermal behaviour of the radiation induced radicals in the copolymers allowed the assumption of two mechanisms responsible for the formation of the thio radicals: First, the formation takes place via ion radicals …