Patented Mar. 7, 1950 2,499,833

UNITED STATES PATENT OFFICE 2,499,833 METEOD OF MARING FLUORNATED ORGANIC COMPOUNDS Melvin A. Perkins, Wilmington, Del, assignor to the United States of America as represented by the United States Atomic Energy Commission No Drawing. Application July 2, 1944, Serial No. 546,916 3 Claims. (C. 260-648) 2 This invention relates to new halogen com silver difluoride to replace hydrogen and saturate pounds and to methods for their production. any residual double bonds. It is an object of the invention to provide prod The products have densities in the neighbor lucts of high thermal stability and inertness to hood of 1.8 and refractive indices of about 1.3 chemical reagents, particularly oxidizing agents, s (sodium-D-line) at 23° C. They are usually ob acids, bases and metals. A further object is the tained in the crude state as mixtures of compounds provision of products suitable for use as heat of the molecular formulae CaF16, CaClF15, CaCl2F14 transfer media, lubricants and Sealants. Further and other chloro-fluorocarbons, from which the objects will appear from the following detailed individual constituents may be obtained by frac description of the invention. tional distillation. The products possess a high In my United States patent application Serial degree of stability to oxidizing agents, acids, bases Number 546,915 entitled "Halogenated organic and metals, and the stability increases with the compounds and method of making,' filed on the degree of fluorination. Thus the compound CaF16 Same date herewith, which became U. S. Patent is the most stable compound of the group and the No. 2,485,507 on October 18, 1949, there is de 5 compound CaClF15 is only slightly less stable. Scribed a process for the manufacture of chlo The products may be used for any purpose for rinated hydrocarbons of the molecular formulae which an inert fluorocarbon or chlorofluorocarbon Csh5CI11, CaF4Cl10, CahaClg and CHgCls by the is suitable. For instance, they may be used in the condensation of trichlorethene with a Prins type crude state or after isolation, as COOlants, Sealants dinner of a dihydroperchloropropene containing O and lubricants, or as reaction media, for con Only One hydrogen atom in 1-position, with or ducting chemical reactions. without Subsequent dehydrochlorination of the In the manufacture of the products of the product. The condensation product has the struc present invention from the products of my United tural formula States patent application Serial Number 546,915, 25 it is preferred to employ a partially dehydrochlo CCC cighchcic CICHC. rinated compound or mixture of compounds hav CCCCs ing an average molecular formula of about Cah: Clg. Compounds containing a greater pro I have now found that the products so pre portion of hydrogen may be used as initial ima pared may be fluorinated by means of fluorinating 30 terials for the fluorination process, but hydrogen agents such as antimony and arsenic pentafluo in the organic compound consumes fluorine to rides, cobalt trifluoride, manganese trifluoride and form hydrogen fluoride and thus the total quantity silver difluoride to produce cyclic fluorocarbons of fluorinating agent required increases with the and chloro-fluorocarbons of the general formula, hydrogen content. Moreover the compounds of CsClaR16-it, in which ac may be zero or a positive 35 higher hydrogen content react violently with a integer less than 12. fluorinating agent such as antimony pentafluoride The fluorinating agents CoF3, MnF3 and AgF2 and the process is accordingly difficult to control. replace hydrogen and Saturate double bonds more Although the dehydrochlorinated products having readily than they replace chlorine. Hence by the average molecular formula CsClg may in treating the initial material with one of these re 40 clude Small proportions of the compounds Ca5O11 agents directly, cyclization products of high chlo and CaCl10, these atter compounds are suff rine content containing five or more fluorine ciently diluted by the more highly dehydrochlori atoms may be produced. By prolonged and nated compounds So that the reaction with anti vigorous treatment with these reagents the chlo mony pentafluoride can be readily controlled. rine content can be further replaced by fluorine. 45 When fluorochlorides of pentavalent antimony The fluorides and the fluorochlorides of pen are used in place of antimony pentafuoride, the tavalent antimony and arsenic, on the other hand, fluorination proceeds with difficulty and only a replace chlorine with greater facility than they minor proportion of the chlorine is replaced by replace hydrogen. Consequently in order to ob fluorine. Consequently, to replace a major pro tain Saturated cyclic compounds of high fluorine 50 portion of the chlorine, the fluorination must be content, which are the preferred products of the continued with antimony pentafluoride. invention, it is desirable to employ an antimony It is preferred to employ the antimony penta Or arsenic fluorinating agents to reduce the chlo fluoride treatment directly upon the dehydrochlo rine content and a reagent of the group consisting rinated compounds without using a preliminary of Cobalt trifluoride, manganese trifluoride and 55 fluorochloride treatment. The antimony penta 2,499,888 3 4. fluoride treatment may be carried out at a tem at 20° C. and a refractive index (sodium-D-line) perature between 100 and 300° C. This treat of 1.33 at 20 C. ment not only effects a replacement of chlorine 27 parts of this oil were vaporized and passed by fluorine, but at the same time effects a cycliza into contact with cobalt trifluoride maintained tion of the compound and at least to this extent, at a temperature between 300 and 320 C. The reduces the number of double bonds present in the product was condensed and comprised 20 parts molecule. The antimony pentafluoride may also of an oil having a density of 1.82 at 24 C. and saturate some of the double bonds by direct fluo a refractive index of 1.31 at the same tempera rination; but ordinarily by a one-step or two-step ture. treatment with antimony pentafluoride, products O The product was washed with water, dried by are obtained which retain a substantial degree of shaking it with anhydrous sodium sulfate, filtered, unsaturation. The antimony pentafluoride treat and distilled at normal atmospheric pressure. ment may replace part of the hydrogen present The following fractions were obtained: by fluorine, but the proportion of the total hydro gen so replaced is Small. The proportion of s (a) Below 70° C., 0.8 parts; chlorine in the product can be controlled by the (b) From 70° to 83° C., 0.5 parts; extent of fluorination in the antimony penta (c) From 83° to 90° C., 0.6 parts; fluoride step. Thus by employing a relatively (d) From 90° to 100° C., 1.0 parts; small proportion of antimony pentafluoride, a (e) From 100° to 110° C., 3.8 parts; product of high chlorine content can be obtained 20 (f) From 110° to 120° C., 2.7 parts; whereas by increasing the proportion of antimony (g) From 120° to 132° C., 3.9 parts; pentafluoride or by employing repeated fluorina (h) Residue above 132° C., 5.5 parts. tions with this reagent, the chlorine content can Fraction (e), most of which distilled at 104 be reduced to a very small value. to 107° C., had a refractive index of 1.304 at The fluorination with cobalt trifluoride, man 25 24.5° C., a chlorine content of 7.4%, and a molecu ganese trifluoride or silver difluoride is preferably lar weight of 377. The low molecular weight conducted at temperatures between 150 and 400° indicates that this product contained decomposi C. with the partially fluorinated material in vapor tion products and was probably a mixture of C8 phase. This finishing treatment not only replaces compounds with C7 and perhaps C6 compounds. all of the residual hydrogen by fluorine but also 30 Fraction (g), which distilled principally in two Saturates residual double bonds so that a satu temperature ranges, the first, 123 to 125 C., and rated cyclic product is obtained. the second, 129 to 132° C., exhibited the follow The final fluorination step to replace hydro ing characteristics: gen may reduce the proportion of chlorine in (a) Refractive index (24.5° C.) : 1.312; those compounds containing relatively high pro 35 (b) Chlorine content: 6.6%; portions of chlorine. However, the final one or (c) Density (24° C.) : 1.79; two chlorine atoms are relatively resistant to the (d) Molecular weight: 415. fluorinating agents employed in this step and From its chlorine content and molecular weight, consequently products containing One or two it is evident that the product consisted of a atoms of chlorine per molecule may be passed 40 mixture of fluorocarbon, CaF16, and fluorocarbon through this finishing step without substantially monochloride, CsClF15, in a ratio of about 1 to 3. reducing their chlorine content, expressed as It Will be understood that I intend to include atoms per molecule. variations and modifications of the invention and The following example will further illustrate that the preceding example is an illustration only the invention. (Quantities are expressed as parts and in no wise to be construed as a limitation by weight.) 45 upon the invention, the scope of which is defined Eacample in the appended claims, wherein I claim: 1. The method of making mixtures of Satu 78 parts of a product having the average rated fluorocarbons and chloro-fluoro-carbons molecular formula CaF2Clg and obtained by de having molecular formulae selected from the hydrohalogenating the condensation product of 50 group C8F16, CsClF15 and CsCl2F14, which com 1,2,3,4,5,5,6,6-Octachloro-n-hexene and trichlor prises reacting an unsaturated chlorine contain ethene in the presence of anhydrous alumi ing aliphatic compound having 8 carbon atoms num chloride as described in my United States selected from the group consisting of an un patent application Serial Number 546,915 were decachloro-Octene having the structural formula mixed with 273 parts of SbF5. 55 The mixture was placed in a nickel bomb which CEC=CC-OH-CHC1-C Cl-CHC was heated for 4 hours at 180° C. in a shaking (Ho-o Ol machine. The product was then allowed to cool and its dehydrochlorination products having the to room temperature. The contents of the bomb molecular formulae CahaCl10, C8H3Clg and Cah:Cl stratified, and the upper organic layer was de (3) with a fluorinating agent selected from the group Canted off from the lower antimony fluorochlo consisting of the pentavalent fluorides of anti ride layer. 64 parts of organic product were ob mony and arsenic to obtain a fluorinated product tained. in which most of the chlorine atoms have been 60 parts of this organic product were mixed replaced by fluorine atoms, and then reacting with 205 parts of fresh SbF5, and the mixture was 35 Said fluorinated product with a fluorinating agent heated in a nickel bomb for 8 hours at 180° C. Selected from the group consisting of cobalt tri in a shaking machine. The bomb was then fluoride, manganese trifluoride and silver di cooled, and the organic product was separated fluoride in order to replace residual hydrogen with from antimony Salts by decantation. 48 parts fluorine and to Saturate residual double bonds of organic product were thus obtained. 70 with fluorine so that a saturated product is ob This product was washed with water, separated tained. from wash-water and dried by mixing it with an 2. The method of making mixtures of Saturated hydrous sodium sulfate. Upon separating the fluorocarbons and chloro-fluorocarbons having Sodium Sulfate, there were obtained 41 parts of molecular formulae selected from the group an amber-colored oil having a density of 1.78 75 CaF16, CsClF15 and CsClaF14, which comprises re

2,490,888 S s acting an unsaturated chlorine containing all- perature between 100 and 300° C. to obtain a phatic product having an average molecular fluorinated product in which all but about one formula of CsCls, which has been obtained by chlorine atom per molecule has been replaced the dehydrochlorination of an undecachloro- by fluorine, and fluorinating the resulting octenehaving the structural formula 5 fluorinated product at a temperature between CHCCC1-CBI-CIO-OC-C-Cl 150' and 400° C. with sufficient cobalt trifluoride thC-C Cls to replace residual hydrogen with fluorine and to saturate residual double bonds with fluorine with antimony pentafluoride at a temperature so that a saturated product is obtained. between 100° and 300° C. to obtain a fluorinated lo MELVN A PERKNS. product in which most of the chlorine atoms have been replaced by fluorine atoms, and then re- REFERENCES (C-E) acting the resulting fluorinated product with a fluorinating agent of the group consisting of The following references are of record in the cobalt trifluoride, manganese trifluoride and silver s file of this patent: difluoride at a temperature between 150 and UNITED STATES PATENT 400° C. in order to replace residual hydrogen with fluorine and to saturate residual double bonds s Dacial a as or - up-n - Jun.1935 with fluorine so that a saturated product is ob- 36.2 Benning ---- Aug. 26, 1947 tained.3. The method of making mixtures of saturated 20 2,456,456037 siS mons ------Dec.8 am14, as 1948 fluorocarbons and chloro-fluorocarbons having FOREIGN PATENTS molecular formulae selected from the group Number Country Date CaFis, CsClF15 and CsCl2F14, which comprises re- 786,123 France ------Aug. 27, 1935 acting an unsaturated chlorine containing ali- 25 phatic product having an average molecular OTHER REFERENCES formula of CshaCls, which has been obtained by Henne et al., "J. Am. Chem. Soc.,' vol. 61, page the dehydrochlorination of an undeca-chloro- 938 (1939). octene having the structural formula Simons et al., "J. Am. Chem. Soc.,' vol. 61, CHCCC-CH-OHCl-O Ol-CHCl 40 pages 2963-6 (1939). &EC-col, Fukuhara et al., "J. Am. Chem. Soc.' vol. 63, with sufficient antimony pentafluoride at a tem- pages 272792-5 (1941)1941).

Certificate of Correction Patent No. 2,499,833 March 7, 1950 MELVIN A PERKINS It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Column 1, line 53, for the word "agents' read agent; column 4, line 55, for that portion of the formula reading “CC-CHC' read CCla-CHCl,; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office. Signed and sealed this 18th day of July, A. D. 1950.

SEAL

JOE E. DANIELS, Assistant Commissioner of Patents.