Abstract: | The free radicals induced in tetraoxane at liquid nitrogen temperatures by 60Co γ-rays have been studied by ESR. The powder spectrum as well as he spectra of the single crystal rotated around the b axis have been studied through their modifications from ?196°C up to + 80°C. These spectra show that at low temperatures two radicals exist conserving the cyclic nature of the parent molecule. During the course of annealing, starting at ?140°C and towards ?85°C they are gradually replaced by radicals with a linear structure, this being the first step in the post-polymerization process of tetraoxane. Further increase in temperature leads to radical sites situated on the polymer chains. At low temperatures evidence has also been found for the formyl radical, radical pairs, and a photo-sensitive radical. |