Chlorotrifluoroethylene oxidation with oxygen

Haszeldine, R. N. et al., J. Chem. Soc., 1959, 1085-1086 1,1,1-Trichloroethane exploded after heating under oxygen at 54 bar and 100°C for 3 h [1], Trichloroethylene, remaining in a pipe after cleaning operations, exploded under 27 bar pressure of oxygen at ambient temperature. It was later found possible to explode stoicheiometric mixtures [2], Chlorotrifluoroethylene and bromotriflu-oroethylene each react explosively with oxygen at ambient temperature [3], but controlled oxidation of the former produces an explosive cyclic peroxide, 4.5-dichloro-3,3,4,5,6,6-hexafluoro-1,2-dioxane [4]. 

Chlorotrifluoroethylene is a colorless gas at room temperature and pressure. It is fairly toxic with an LC50 (rat), 4 hr of 4000 ppm. It has a critical temperature and pressure of 105.8°C and 4.03 MPa. Oxygen and liquid CTFE react and form peroxides at fairly low temperatures. A number of oxygenated products are generated by the oxidation of chlorotrifluoroethylene, such as chlorodifluoroacetyl fluoride.The same reaction can occur photochemically in the vapor phase. Chlorotrifluoroethylene oxide is a by-product of this reaction. The peroxides act as initiators for the polymerization of CTFE, which can occur violently. 

CHLOROTRIFLUOROETHYLENE (79-38-9) Flammable gas. Forms explosive mixture with air (flash point — 18°F/—28°C). Unless inhibited (terpenes 1% tributylamine are recommended), this material forms unstable peroxides. Reacts violently with oxidizers, bromine, chlorine, chlorine perchlorate, fluorine, ethylene, dichloroethylene, oxygen. Incompatible with chlorine trifluoride, vinylidene chloride. 

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