The basis features of the mechanism of the γ-radiolysis of perfluoropolyethers of general formula Rf(CF2CF2O−)n(CF2O−)mRf and RfO[CF2CF(CF3)O−]n(CF2O−)mRf have been elucidated by ESR analysis of the adducts of the intermediate radicals. According to the species identified the major radiolytic processes are based on C-C and C-O bond ruptures resulting in chain degradation. Of minor importance is the cleavage of C-F bonds. A reaction mechanism is proposed.
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