The paper describes the results of studies of the peculiarities of thermal behavior of low-molecular fractions of low molecular PTFE obtained by sublimation of the powder of under isothermal conditions at 50 - 100°C. The peculiarities of fractions transition into the gas phase at heating are studied by IR spectroscopy. The IR spectroscopic and the quantum chemistry data are interpreted as degradation of polymers. The calculation data provide grounds to assume the presence of small molecules and radical structures in gas phase. The radical fragments are formed in the gas phase as a result of the polymer chains thermal destruction and provide the structure recovery until initial state during the subsequent condensation of the sample.

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