The reactions of perfluorinated α- and β-alkoxyradicals with hydrogen chloride, chlorine and fluorine

The kinetics of the reactions of the macroradicals Rf′OCF2 (I) and Rf′OCF2CF2 (II) with HCl, Cl2 and F2 have been studied in the liquid phase, being Rf′ a poly(oxydifluoromethylene-oxytetrafluoroethylene) chain with average molecular weight of about 104 Da. Radical (I) showed a higher reactivity compared to radical (II) with all the three radical transfer agents. e of HCl the activation energy for the reaction:Rf+HCl→kTRfH+Clwas estimated for both the macroradicals. A value of activation energy Ea=6.5±1.1 kcal/mol was obtained for radical (II), in good agreement with the value reported for the CF3 radical in the gas phase [Trans. Faraday Soc. 62 (1966) 1662] whereas an activation energy of about 2 kcal/mol was estimated for radical (I). perimental results indicate a strong effect of the α-oxy substitution on the reactivity of the perfluorinated radical. This effect is discussed in terms of polarity of the transition state.