An e.s.r. study of the motion of peroxy radicals in isotactic and atactic polypropylenes

E.s.r. spectra of peroxy radicals trapped in isotactic and atactic polypropylenes have been observed at various temperatures. The spectrum observed at 77 K was shown to be composed of one component by comparing it with that at 4 K. The spectra observed at higher temperatures comprised of two spectra arising from the rigid peroxy radicals and the mobile peroxy radicals. All of the observed spectra have been reconstructed by means of computer simulation and the changes in anisotropic g-values with temperature were estimated. The motion of the mobile fraction was shown to be rotation or rotatory vibration of the radicals around the chain axis both in the isotactic polypropylene and in the atactic polypropylene as well as in polyethylene and poly(tetrafluoroethylene) although the structures of the polymers are different, that is helical (polypropylene) or planar zigzag (polyethylene, poly(tetrafluoroethylene)).