Patent GB-863406-A (GB)
Title: Improvements relating to the production of thiocarbonyl fluoride
IPC: C01B17/45
Filed: 1959-09-01
Abstract: In the preparation of thiocarbonyl fluoride by heating CS2 with a binary fluoride of carbon, silicon, nitrogen phosphorus, oxygen, or sulphur, at at least 1500 DEG C. (see Group III), fluorocarbons e.g. CF4, C2F6, C2F4, and saturated or unsaturated fluorocarbons containing 3 or more C atoms, and perfluoromethyl sulphides are also referred to as being produced.  Fluorides may be SiF4, NF3, PF5, OF2, SF4, SF6, CF4, C2F6, or C2F4, and 0,1-10 moles CS2 may be used per mole fluoride.  Subatmospheric pressure e.g. 10-300 mm. Hg. is preferred, but atmospheric and superatmospheric pressures may be used.  Products may be subjected to normal cooling or may be rapidly cooled say to 400-500 DEG C. in 1/10 th sec.  The reactant vapours with a carrier gas e.g. N2, He, or A, may be passed through a refractory tube, which may be packed with refractory, e.g. carbon, chips, heated by a resistance, or induction, furnace.  Alternatively, the reactants with a carrier gas may be heated by an electric arc in contact with the arc flame at 2,500-4,000 DEG C., or out of contact with the arc flame at 2,000 DEG C.  Preferred heating is by magnetically rotated arcs.ALSO:<PICT:0863406/III/1> Thiocarbonyl fluoride, CSF2, is prepared by heating CS2 with a binary fluoride of carbon, silicon, nitrogen, phosphorus, oxygen, or sulphur, at at least 1500 DEG C.  Fluorides may be SiF4, NF3, PF5, OF2, SF4, SF6, CF4, C2F6, or C2F4 and 0.1-10 moles CS2 may be used per mole fluoride. Subatmospheric pressure e.g. 10-300 mm.  Hg. is preferred, but atmospheric and superatmospheric pressures may be used.  Products may be subjected to normal cooling or may be rapidly cooled say to 400-500 DEG C. in 1/10 th.  The reactant vapours with a carrier gas, e.g. N2, He, or A, may be passed through a refractory tube, which may be packed with refractory, e.g. carbon chips, heated by a resistance, or induction, furnace.  Alternatively, the reactants with a carrier gas may be heated by an electric arc in contact with the arc flame at 2500-4000 DEG C., or out of contact with the flame at 2000 DEG C. Cu, W, carbon, or graphite electrode may be used, and may be cooled. Preferred heating is by magnetically rotated arc operating at 10-75 volts and 20-700 amps.  As shown, reactants, with or without a carrier gas, enter water-jacketted copper tube 6 containing graphite cathode rod 8 and pass through perforations 7 into water-jacketted silica glass reaction chamber 1.  The gases pass through the arc struck between cathode 8 and graphite sleeve anode 10 mounted in water cooled copper ring holder 11.  Reaction products are withdrawn through pipe 13 in the quench section, in contact with open-topped copper vessel 12 containing water, solid CO2, or liquid N2, to cold traps.  The arc is rotated by the magnetic field generated by solenoid magnet 20.  Alternatively, Fig. 2 not shown, the reactants pass through an annular channel in a cup-shaped anode, out of contact with the flame.  The product gases contain CSF2, S, the free element of the fluoride, or compounds thereof, fluorocarbons, and unreacted CS2 and fluoride which are recycled.  When nitrogen is used cyanogen and cyanogen fluoride are also formed.  The fluorocarbons formed include CF4, C2F6, C2F4, and saturated or unsaturated fluorocarbons containing 3 or more C atoms.  Other products specifically mentioned are perfluoromethyl sulphides, PF3, and POF3.