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The action of accelerated 1–4-MeV protons on polychlorotrifluoroethylene in vacuum was accompanied by a preferential rupture of the main polymer chain with the release of more than 30 gaseous products, most of which were tetrafluoroethylene and chlorine- and fluorine-containing compounds. As a result of proton bombardment, the concentration of carbon on the polymer surface decreased and the concentrations of fluorine and chlorine increased. It has been shown that the incorporation of chlorine atoms into the structure of a perfluoropolymer changes the mechanism of its proton bombardment and helps to protect its macromolecule from the reaction of fluorine abstraction by accelerated protons with the formation of hydrogen fluoride. It has been found that irradiation with accelerated protons leads to changes in surface energy characteristics. [ABSTRACT FROM AUTHOR]