High molecular weight polymeric perfluorinated copolyethers and process

Abstract

Amorphous, highly viscous high molecular weight copolyethers containing in excess of 200 total repeating units and formed of --CF.sub.2 --CF.sub.2 --O-- and --CF.sub.2 --O-- repeating units randomly distributed along the chain and linked to each other either directly or through an oxygen atom, in which latter case a peroxy group is present along the chain. These copolyethers, which are useful for preparing bifunctional telomers, high molecular weight fluoropolymers, and highly stable lubricants and heat exchange materials, are prepared by reacting molecular oxygen with tetrafluoroethylene dissolved in a fluorinated or chlorofluorinated solvent selected from the group consisting of dichlorodifluoromethane, perfluorocyclobutane, perfluorodimethylcyclobutane, 1,2-dichloro-hexafluoropropane and 1,2-dichloro-tetrafluoroethane in the presence of ultraviolet radiation and under such conditions that the molar ratio of the tetrafluoroethylene to the oxygen in the reactant feed is between about 0.1 and 2, the reaction temperature is between about -80.degree. C. and -35.degree. C., the total pressure at the point where the gaseous reactants are introduced into the reaction zone is between about 1 and 2 atmospheres, and the ratio F/VE is greater than 3.0.times.10.sup.-4 (mols./cc. watt hour) where F is the number of mols/hour of tetrafluoroethylene fed to the reaction zone, E is the number of watts of ultraviolet rays having a wave length below 3,300 .ANG. which penetrate the reaction zone, and V is the volume of the reaction zone.