o Patented June v30, ‘1942 I 2,287,934 UNITED‘ Q MANUFACTURESTATES sgggim-nmnocm- PATENT- Q I.OFFICE Mam v. Grosse and Carl‘. B. Linn, Chicago, assignors to Universa 1 Oil Products Company,111., _ . _ Chicago, Ill., a corporation of Delaware. I No Drawing. Application October 31’, 1938, ' Serial No. 238,051 , ' I , J '1 Claims. (01. 260-653) This invention relates particularly to the man- ' the abstraction of the heat ofv reaction so that ufacture of compounds having the general for the temperature is not allowed to rise above a mula, R—CF2—-R' in which R may be an alkyl ?xed point. As will be shown in later numerical radical suchv as CH3, CzHs, etc., R’ ‘may be a examples, it is necessary to maintain a consider-v hydrogen atom or an alkyl radical, and the other able excess of .hydrogen fluoride at all times to letters have the values commonly assigned to‘ , eliminate the tendency'of theacetylene hydro them as representing chemical elements. carbons to polymerize and insure the direct ad The invention is more speci?cally ‘concerned dition of hydrogen ?uoride as a predominating with the manufacture of the above compounds reaction. When‘ the proper amount of acety under particular conditions in respect to ‘tem lene hydrocarbon has been introduced and there perature control so that side reactions are min is still .an excess of liquid hydrogen ?uoride, op imized and practical yields of the desired prod erations are stopped and the upper layer of fluo_ ucts are obtained. ‘ ' ride is withdrawn. Obviously the operation may Compounds of the above general formulaare be made continuous by providing means for the known as di-?uoro-para?ins and are completely controlled addition of both the acetylene hydro stable in that they do not split oil?‘ hydrogen carbon and the hydrogen fluoride at, one point ?uoride on ‘standing under ordinary tempera _ in a reaction vessel and separation of the two a ture and pressure conditions or during distillation . layers at another point withithe return of'un as do some alkyl ?uorides, especially tertiary converted» hydrogen fluoride. ; ' ?uorides. The compounds have generally‘ a ~ ‘The products" of the reaction are washed with pleasant odor and are utilizable as refrigerating liquids. alkaline materialsand dried with calcium..chlo ride and distilled for a ?nal puri?cation." In one specific embodiment the‘ present in The typical reaction involved in the presentin-v vention comprises the manufacture of di-iluoro stance is’shown by the following equation: para?ins by reacting hydrocarbons of the acet-, ylene series of-higher molecular weight than R-—CECI—R’+2HF __» R~g—cm—u' '_ acetylene with liquid anhydrous hydrogen ?uo Y 2 The reaction is characteristic of all compounds The operations by which the compounds of _ of the acetylene series except acetylene itself up the invention are prepared are relatively simple. to the point where difiiculties are encountered by v the solidi?cationof the higher molecular weight , In batch or intermittent processes, hydrogen ?u members of the series or the iluorinated products - orideis lique?ed and brought to the proper re at the necessary temperatures of the reaction, ,action temperature in a vessel surrounded by a and under these circumstances, the use of hy heat-absorbing bath, such as, for example, a drocarbon solvents may be resorted to. mixture of acetone and carbon dioxide, in case 1 The following numerical data is given to illus operations are conducted at low temperatures trate the scope of the invention, but it is not in ' _ of the order of 0° C. or lower. While the desired tended that the invention be‘in any way limited reactions will take place to produce substantial I yields of di-?uoroépara?ins at temperatures up thereby. ‘ _ A number of runs were conducted on different to the normal boiling point of hydrogen ?uoride, hydrocarbons, the results of which are sum to wit, +20° 0., low temperatures favor more ‘ marized in the following table: \ Propyne Hexyne-l Hcxyno~3 Hcptyne-l Alk?ie charged: . ols__.__ 0.47 0.212 0. 361 0.297 , ' Grams . _ . _ . _ _ _ _ ._ 19 17.4 - 29.6 ~28. 5 Temp. reaction _° 0.. —66 to -7l- —55 to -60 —65 try-70 —40 to —70 Time of addition of hydrocarbon ______ _;minutes_. 90 - 70 70 65 Hydrogen ?uoride charged: _ ' Mols _________________________________ __' ..... __ 4. 30 2.17 3. 57 4, 85 Gram; _______________________________________ _ _ 86. 0 43. 4 71. 5 97.1 Crude, water insoluble roduct recovercdgmms. _ 23. 3 22.1 39. 4 34. 5 Concentration of pure i-?uoride in crude product . as shown by distillation __________ _.wt. percent" 100 79 35 60 Yield di-?uoride based on alkyne charge__pcrcont. 61 68 76 52 selective reactions over those resulting from‘ Mt . In all cases . there ‘was some production of ' polymerization. In practical operations, copper amorphous solid materials produced by the poly- : linedsvessels have been found to give the best merization of the acetylene hydrocarbons, but service. The acetylene hydrocarbon is then these were heavy and readily separable from the slowly introduced below the surface of the lique-' desired reactant products. - e - fied hydrogen ?uoride at a rate which permits co‘v The following tabulation shows a comparison of 2 2,287,934 hexanes-which comprises gradually introducing the-properties of the. products as reported previ-_ hexynes into substantially anhydrous liquid hy ously in the chemical literature'and as produced, drogen ?uoride at a temperature ,below 0° C., and shows that the products of the reaction were ' substantially pure. while abstracting heat of reaction to prevent sub ' Propyne Hexyne-l Hexyne'tl Hepty’ne-l Reactants, HF+ ' - Product , 2, Z-di-?uoro propane - 2, Z-di-?uoro hexane . 3, a-di-?uoro hexane ~ 2, 2-di-?uoro heptane Report. Prod. Report. _ Prod. ’ Report. > Prod. Report. Prod. Properties:Percent H ..... _. 7.> 56 7. 54 9. 46 9. 91 10.32 _ 44. 97 45. 00 56. 42 58. 97 61. 51 47. 47 47. 00 - 34. 12 31. 12 v 28. 17 80. 05 77 122 122. 10 ' 134 mm —0. 5°l755 mm. 86. l°l750 mm. ________ __ 86 0°l742 mm 111. 1°I740 mm. - 1.3118 _ 1. 353B -__.\ ____ ._ 1. 35 1. 3651 —42. 5° +20. 0° ........ __ +20. 0° +21. 5° 1. 03 at ---80 ________ __ . 8918 ________ ._ . .8880 —104.8 ............................................................................... .. We claim as our invention: . stantial temperature rise, and ' maintaining a l. A process for the manufacture of di—?uoro- molal5. A excess process of hydrogenfor the manufacture ?uoride. ' of cli-?uoro- paraf?ns which comprises interacting a member heptanes which comprises gradually introducing of the acetylene series of higher molecular weight 25 heptynes into substantially anhydrous liquid hy than acetylene with a molal excess of substan drogen ?uoride at a temperature below 0° C., tially anhydrous liquid hydrogen ?uoride at a while abstracting heat of reaction to prevent sub temperature below the boiling point of hydrogen stantial temperature rise, and maintaining a ?uoride. ' ‘ molal excess of hydrogen ?uoride. ' 2. A process for the manufacture of di-?uoro 6. A process for producing di?uoro-paraiilns para?ins which comprises gradually introducing which comprises reacting a hydrocarbon'of the a liquefied member of the acetylene series of hy acetylene series and of higher molecular weight drocarbons of higher molecular weight than acet-' than acetylene with substantially anhydrous ylene into substantially anhydrous liquid hydro liquid hydrogen ?uoride at. a temperature not ap , gen ?uoride at a temperature below the boiling ‘35 preciably in excess of 0° C. while imaintaining a point of hydrogen ?uorid e, while abstracting heat molal excess of hydrogen ?uoride. of reaction to prevent ‘s ubstantial temperature _ 7. A process for producing di?uoro -para?ins rise, and maintaining a molal excess of hydro gen which comprises introducing to a reaction zone. a ‘hydrocarbon_ of the acetylene series an d of . fluoride. , 3. A process for the manufacture of 2,2'-di?uo 40 higher molecular weight than acetylene and a_ ro-propane which comprises gradually introduc molal excess of substantially‘ anhydrous liquid ing propyne into substantially anhydrous liquid hydrogen ?uoride, reacting said hydrocarbon with hydrogen ?uoride at atemperature below 0° C., hydrogen ?uoride in the reaction zone, and ab stracting su?icient heat from'said zone to main while abstracting heat of reaction to prevent sub 45 t'ain thereina reaction temperature below 0° C. stantial temperature rise, and maintaining a ' ‘ ARISTID V. GROSSE. molal excess of hydrogen ?uoride. ' CARL B. LINN. ' 4. A process for the manufacture of di-?uoro- _ .