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United States Patent (19) (11) 3,799,996 Bloch (45) Mar

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United States Patent (19) (11) 3,799,996 Bloch (45) Mar United States Patent (19) (11) 3,799,996 Bloch (45) Mar. 26, 1974 54). PREPARATION OF 3,016,405 1/1962 Lovejoy........................... 260/653.3 TETRAFLUOROETHYLENE 75 Inventor: Herman S. Bloch, Skokie, Ill. Primary Examiner-Daniel D. Horwitz 73) Assignee: Universal Oil Products Company, Attorney, Agent, or Firm-James R. Hoatson, Jr.; Ray Des Plaines, Ill. mond H. Nelson 22 Filed: Aug. 4, 1971 (21 Appl. No.: 169,046 57 ABSTRACT Tetrahalo-substituted ethylenes, and particularly tetra 52) U.S. Cl............................... 260/653.3, 252/443 fluoroethylene, may be prepared by reacting a mixed (51 Int. Cl........................ C07c 17/26, CO7c 2 1/18 tetrahalomethane with a metal carbonyl in the pres 58) Field of Search.................................. 260/653.3 ence of an inert solvent. The tetrafluoroethylene which is prepared is useful as a starting material for (56 References Cited the preparation of polymeric substances. UNITED STATES PATENTS 2,925,446 2/1960 Drysdale.......................... 260/653.3 9 Claims, No Drawings 3,799,996 1 2 PREPARATION OF TETRAFLUOROETHYLENE fluoromethane, said compounds having been formed This invention relates to a process for preparing tet by any means known in the art. In the present process rahaloethylenes. More specifically, the invention is these compounds are treated with a metal carbonyl concerned with a process for preparing tetrafluor compound under reaction conditions hereinafter set oethylene by utilizing a mixed tetrahalomethane as the forth in greater detail. The metal carbonyls which are starting material, said methane containing two fluoro used to treat the aforementioned dihalodifluorome atoms as well as two halo substituents of a dissimilar na thane preferably comprise carbonyls of metals of ture. Group VIII of the Periodic Table and specifically co Tetrahalo-substituted ethylenes, and more specifi balt carbonyl, nickel carbonyl, and iron carbonyl. The cally, tetrafluoroethylene may be utilized as starting O reaction conditions which are utilized to prepare the materials in the preparation of homo- polymeric sub desired tetrafluoroethylene include reaction tempera stances and of copolymers. A specific example of this tures ranging from subambient, that is, from about 10 is the preparation of polymers known in the trade as C., up to about 100 C. or more. In addition, it is also Teflon. The resultant polymers will find a wide variety contemplated that the process of this invention may be of uses in commercial applications. For example, the 15. effected by utilizing pressures in the range of from polymer may be prepared as a thin coating for cooking about atmospheric up to about 100 atmospheres or utensils such as frying pans or pots whereby the prob more. When superatmospheric pressures are em lem of food adhering to the surface of the cooking ployed, the pressures are afforded by the introduction utensil is eliminated. In addition, the tetrafluor of an inert gas such as nitrogen into the reaction zone. oethylene which may be in the form of a polymer, plas In addition, it is also contemplated that the reaction is tic, or resin, is available as resin powder or may be effected in the presence of an inert organic solvent. formed into sheets, rods, tape, and as an aqueous dis Solvents which may be employed will include dimethyl persion or film. The various forms of the polymeric ma ether, diethyl ether, dipropyl ether, diisopropyl ether, terial, in addition to its use as a coating for cooking methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl utensils where stickiness must be avoided, may also be 25 alcohol, etc., dioxane, tetrahydrofuran and the like. used as gaskets, seals, components for electrical insula The process of this invention may be effected in any tion, linings for drums and containers, valve seats, bear suitable manner and may comprise either a batch or ings and packings, as a spacer for coaxial cables, lami continuous type operation. For example, when a batch nates, diaphragms, molder parts of pumps and fittings, type operation is used, the quantity of the metal car tubes or hoses, etc. The various uses of polytetraflu 30 bonyl such as cobalt carbonyl along with the predeter oroethylene stem from the physical properties of the mined inert solvent is placed in an appropriate appara polymer such as its being nonflammable as well as tus such as an autoclave of the rotating or mixing type. highly resistant to oxidation and the action of chemi Following this, the dihalodifluoromethane such as di cals which include strong acids, alkalis, and oxidizing chlorodifluoromethane is charged to the reactor which agents. 35 is thereafter heated or cooled to the desired operating It is therefore an object of this invention to provide temperature. In addition, if an additional pressure is de a novel process for preparing tetrafluoroethylene by sired, nitrogen is pressed in until the desired operating utilizing a tetrahalo-substituted methane as the starting pressure is reached. Following this, the autoclave is material. maintained at the desired operating conditions of tem In one aspect an embodiment of this invention is 40 perature and pressure for a predetermined period of found in a process for the preparation of tetrafluor time which may range from about 0.5 up to about 10 oethylene which comprises reacting a dihalodi hours or more in duration. At the end of this time, the fluoromethane with a metal carbonyl at reaction condi maintenance of the autoclave at subambient or ele tions, and recovering the resultant tetrafluoroethylene. vated temperatures is dicontinued and the apparatus is 45 allowed to return to room temperature. Any excess A specific embodiment of this invention is found in pressure which may still be present is discharged and a process for the preparation of tetrafluoroethylene the apparatus is opened. The reaction mixture is recov which comprises reacting dichlorodifluoromethane ered and subjected to conventional means of separa with cobalt carbonyl at a temperature in the range of tion which include filtration, washing, drying, extrac from about 20 to about 100° C. and a pressure in a tion, fractional distillation, etc., whereby the desired range of from about atmospheric to about 100 atmo tetrafluoroethylene is recovered and removed to stor spheres in the presence of ethyl ether, and recovering age, the resultant tetrafluoroethylene. It is also contemplated within the scope of this inven Other objects and embodiments will be found in the tion that the process may be effected in a continuous following further detailed description of the present in 55 type of operation. When this type of operation is used, vention. the dichlorodifluoromethane is continuously charged As hereinbefore set forth, the present invention is to a reaction zone which is maintained at the proper concerned with a process for preparing a tetrahalo operating conditions of temperature and pressure, said substituted ethylene in which the halogen substituents reaction zone containing the desired metal carbonyl of are identical in nature. The process is effected by treat 60 the type hereinbefore set forth in greater detail. If so ing a tetrahalo-substituted methane which possesses desired, the solvent in which the reaction is effected the generic formula: may be charged to the reaction vessel through a sepa rate line or the dihalodifluoromethane may be admixed XCF, with the solvent and the combination charged thereto in which X is a halogen other than fluorine and prefera 65 in a single stream. Upon completion of the desired resi bly chlorine or bromine, for example, dichlorodi dence time, reactor effluent is continuously withdrawn fluoromethane, dibromodifluoromethane, diiododi and the gas phase comprising the tetrafluoroethylene is 3,799,996 3 4 separated from any solvent and metal carbonyl, the lat ter two being recycled to the reaction zone while the EXAMPLE II desired product is recovered and removed to storage. In like manner 13 g. of nickel carbonyl and 100 cc. of diethyl ether are placed in the glass liner of a rotating The following examples are given to illustrate the autoclave. The liner is thereafter sealed into the auto process of the present invention which, however, are clave and 0.2 mols of dichlorodifluoromethane is not intended to limit the generally broad scope of the charged thereto. The autoclave is heated to a tempera present invention in strict accordance therewith. ture of 70° C. and maintained thereat for a period of 6 EXAMPLE I hours. At the end of this time, the autoclave is allowed 10 to return to room temperature. Upon opening the auto In this example, 15 g. of cobalt carbonyl along with clave, the reaction product is recovered therefrom, the 100 cc. of diethyl ether are placed in the glass liner of gas phase is separated from the liquid phase, and the a rotating autoclave. The liner is sealed into the auto desired product comprising tetrafluoroethylene is re clave and 0.2 mols of dichlorodifluoromethane are covered from said gas phase. charged to the autoclave. The autoclave is then heated 5 I claim as my invention: to a temperature of 50° C. and maintained thereat for . A process for the preparation of tetrafluor a period of about 4 hours. At the end of this time heat oethylene which comprises reacting a dihalodi ing is discontinued and the autoclave and contents fluoromethane in which the halo substituent is chlo thereof are allowed to cool to room temperature. The rine, bromine or iodine with a carbonyl of a metal of reaction mixture is recovered and the gas phase is sepa Group VIII of the Periodic Table at a temperature in rated from the liquid phase. The gas phase which com the range of from about 10 to about 100° C. and a prises tetrafluoroethylene as well as unreacted dichlo pressure in the range of from about atmospheric to rodifluoromethane is water-washed, dried and fraction about 100 atmospheres.
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