Abstract
Abstract The ESR spectra from polychloroprene uniaxially deformed at 77 K in an oxygen environment are composite spectra arising from two radical species. An allyl radical species results from main-chain rupture midway between the α-methylene groups, and a peroxy radical species is formed by reaction of the oxygen in the environment with the allyl radical species. The stability of these allyl radicals with respect to oxygen and temperature is apparently similar to the allyl radicals formed in polybutadiene and polyisopropene. At liquid nitrogen temperature all the radicals were stable. The peroxy radical species is unstable as Tg is approached and decays to give a resonance-stabilized allylic species, which is stable until the temperature of the sample is slightly above Tg. Above Tg a broad singlet is observed, and it is attributed to a polyenyl radical species.
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