RADIATION CHLORINATION OF PERFLUOROOLEFINS

A spontaneous addition of chlorine is not observed in equimolar mixtur es of perfluoroolefins with chlorine in the temperature range of 70-30 0 K. The radiolysis of these mixtures leads to a vigorous chlorination reaction G(-Cl2) almost-equal-to 10(4) with a thermal effect for tetr afluoroethylene and hexafluoroethylene of 167 +/- 4 kJ/mole. The main radiolysis product is a dichloride. Screening of the radical center by trifluoromethyl groups in the molecule of perfluoroisobutylene leads to a decrease in the intensity of chlorination in comparison with tetr afluoroethylene and hexafluoropropylene.