CATALYTIC FLUOROOLEFIN TRANSHALOGENATIONS

Abstract: Catalyzed halogen exchange between perhaloolefins to form products of the formulas: R¹R²C=CR³R⁸ and R⁵R⁶C=CR⁷R⁴ wherein R¹, R², R³, R⁵, R⁶ and R⁷ are independently selected from F, Cl, Br, C₁ to C₄ perfluoroalkyl and pentrafluorophenyl; or R¹ and R³ together, R² and R³ together, R⁵ and R⁷ together or R⁶ and R⁷ together, when both groups are in the cis configu­ ration, may also represent perfluoroalkylene of 2 to 4 carbons or o-C₆F₄(-)CF₂-; R⁸=F; R⁴ = Cl or Br; none of the fluoroole­ fins simultaneously contain both Cl and Br; and R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ may be chosen as to product identical structures for the reactants or for the products.

Description: TITLE CATALYTIC FLUOROOLEFIN TRANSHALOGENAT IONS This invention concerns transhalogenation between fluoroolefins. This type of exchange reaction, a special case of which is known as disproportionation. has been employed in the art primarily with chlorofluoroalkanes but not with fluoroolefins. One exception. U.S. Patent 3,081.358. discloses the disproportionation of alkenes. specifically chloropentafluoropropenes. to hexafluoropropene and 1.1-dichlorotetrafluoropropene-1 in the presence of a specially prepared aluminum fluoride catalyst. That catalyst is not employed in the process of this invention. A number of publications disclose the more common disproportionation of chlorofluoroalkanes. Those which use an alumina or aluminum fluoride catalyst include U.S. Patents 3.087.976. 2,767,227. 2.637,748. 2,478.932, 2,676,996. and 2,478,201. Other catalysts that have been employed in the disproportionation of alkanes include: Alumina activated by pretreatment with a fluorochloroalkane or hexafluoropropene: U.S. Patents 3,138.559. 3.087.975. and 3,087.974 and Japanese 43-27748; Aluminum chloride on alumina: U.S. Patent 2,694.739; Aluminum fluoride which contains selected amounts of zinc. chromium. nickel and iron: U.S. Patents 3.793.229. 3.787.331 and 3,650,987; Chromium oxide on activated carbon: E. German 117,444; Zinc spinel: Russian 636,216; Copper aluminate spinel: Russian 555,080: Zirconium tetrachloride: Chem. Abstracts 101. 130215 (1984); Zinc, cadmium and mercury: Chem. Abstracts 82, 155162 (1975); Copper: Chem. Abstracts 85, 93718 (1976); Activated carbon and chromium oxide: U.S. Patent 4,192,822; Aluminum fluoride which contains nickel and titanium: U.S. Patent 4,069,266; Chromium fluoride: U.S. Patent 3,651,156; Chromium oxyfluoride: G.B. 1,369,870; Aluminum chloride: West German 1.618,588; and Activated carbon: U.S. Patent 2,981,763. This invention concerns an improved process for continuously preparing by transhalogenation two fluoroolefins of the formula: R 1R2C=CR3R8 and R5R6C=CR7R4 which process comprises reacting at 100-4000C. at a contact time of 0.001-10 seconds, a perhaloolef in of the formula: R 1R2 C=CR 3R4 with a perhaloolefin of the formula: R5R6C=CR7R8 in the presence of a solid catalyst. as charged to the reactor, selected from the group consisting of: A. chromium oxide alone or in combination with one or of RH , Ru , Ir , Pd , Pt AgO. phosphorous oxide, silicon oxide, boron oxide or an oxide or halide of aluminum, manganese, zinc, iron, rhodium, nickel, palladium. cobalt. platinum. cerium. silver. copper. lead. bismuth, iridium, magnesium. barium, tin, lanthanum, calcium, ruthenium. iridium, zirconium, vanadium, molybdenum, or tungsten. B. aluminum oxide in combination with one or more of RH , Ru , Ir , Pd , Pt , Ag , silicon oxide, phosphorous oxide, boron oxide or an oxide or halide of manganese, zinc, iron, rhodium, nickel, palladium, cobalt, platinum. cerium. silver, copper, lead. bismuth, iridium, magnesium, barium, tin. lanthanum, calcium, ruthenium. iridium, zirconium, vanadium, molybdenum. or tungsten. wherein: RÚ. R2. R3. R5, R6 and R7 are individually selected from the group F, Cl, Br, C to C4 perfluoroalkyl, and pentafluorophenyl; or. R1 and R3 together or R2 and R3 together, or R5 and R7 together, or R6 and R7 together, can be selected, when both are in the cis position, from the group consisting of perfluoroalkylene of 2 to 4 carbons and o-C6F4(-)CF2-, i.e. EMI3.1 R8=F, R4 = Br or C1; and wherein none of the reactants or products simultaneously contain both C1 and Br. and R1. R2. R3. R4 R5. R6. and R7 may be chosen as to produce identical structures for the reactants or products. The present invention provides a process for transhalogenation of perhalogenated olefines which is characterized by lower process temperatures and increased throughput due to the greatly improved catalytic efficiency of the heterogeneous catalysts employed. Transhalogenation can be represented by the reaction: EMI4.1 RÚ, Rê, R , R4, R5, R6 and R7 may be chosen such that both R1R2C=CR3R4 and R5R6 C=CR7R8 are the same molecule. In this case when subjected to reaction conditions the molecule produces two distinct products for R1R2C=CR3R8 and R5R6C=CR7R4. This special case of transhalogenation is referred to as disproportionation. In addition R1. R2. R3. R4, R5. R6 and R7 may be chosen such that both R1R2C=CR3R4 and R5R6C=CR7R8 represent two distinct molecules and when subjected to reaction conditions would produce identical structures for R1R2C=CR3R8 and R 5R6C=CF7R4. This special case of transhalogenation is referred to as conproportionation. The following equations represent particular examples of disproportionation. The reverse are examples of conproportionation. EMI4.2 In each example of disproportionation. a perhaloolef in more highly fluorinated on the carbon-carbon double bond than the starting perhaloolefin is obtained. The coproduct obtained is correspondingly less fluo-rinated than the starting perhaloolefin. Subsequent recycle of the coproduct by fluorination by known methods. e.g.. those disclosed in U.S. Patent 3,878,257, will give the starting perhaloolefin which can be recycled in the disproportionation reaction. Thus, highly or completely fluorinated olefines can be readily obtained by the process of this invention. As used throughout the specification. the terms "halo" and halide refer to F, C1. and Br. Preferred fluoroolefin products are perfluoroolefins. Especially preferred perfluoroolefins are tetrafluoroethylene and hexafluoropropylene. Preferred perhaloolef in reactants are those which contain up to about 10 carbons, most preferably up to 6 carbons. Transhaloaenation Catalysts Catalysts suitable for charging to the reactor in the process of the present invention are solid catalysts comprising supported metals. metal oxides or halides preferably selected from transition elements and rare earth elements. It is preferable that the chlorides, bromides and fluorides of the metal be relatively high melting. i.e., have a melting point above about 4000C. The melting points of such chlorides and fluorides are given by Glassner, U.S. government publication ANL-5750, "The Thermochemical Properties of the Oxides, Fluorides, and Chlorides to 25000K'1, Argonne National Laboratory. Preferred catalysts are those that contain Cr203, supported on alumina or unsupported. and MnO on alumina. Cr2O3 is particularly preferred. The term "oxide" and "halide11 includes binary. ternary. quaternary, and higher polynary oxides and halides as well as solid solutions and non-stoichiometric oxides and halides. It includes a single oxide or halide; mixed oxides or halides of a single metal in different valence states such as FeO and Fe2O3, the corresponding chlorides, and the like; as well as mixed oxides or halides of different metals such as physical mixtures of iron oxide and manganese oxide. the corresponding chlorides. and the like. In the case of ruthenium, rhodium, iridium, palladium, platinum, and silver oxides and halides, the terms "oxide" and "halide also refer to the products derived by calcination of such compounds, which can be the elemental forms of such metals, either singly or in combination with corresponding oxides and halides. Representative catalysts of Group A include chromium sesquioxide (Cr203) alone or in combination with one or more of RhO, RuO. IrO. Pd , PtO, AgO, iron oxide, palladium fluoride, platinum chloride. cobalt oxide, nickel oxide, rhodium chloride, rhodium bromide, ruthenium chloride, iridium chloride, copper oxide, phosphorus pentoxide. boron oxide, barium oxide, lanthanum oxide, calcium oxide, zirconium oxide, cerium oxide, silver fluoride, copper oxide, copper chloride. manganese oxide, lead oxide, bismuth oxide, iridium chloride, magnesium oxide, silicon dioxide, tin oxide, vanadium oxide, molybdenum oxide or tungsten oxide. Representative catalysts of Group B are aluminum oxide in combination with one or more of Rh0. Ru , Ir , Pd , Pt , Ag , manganese oxide, silicon dioxide, zinc oxide, zinc chloride, iron oxide, iron chloride, rhodium chloride, nickel chloride. nickel oxide, palladium oxide, palladium chloride, palladium fluoride. cobalt oxide, platinum chloride, platinum oxide, cerium oxide, silver fluoride, silver bromide, copper oxide. copper chloride. lead oxide. bismuth oxide, iridium chloride, phosphorus pentoxide. magnesium oxide. boron oxide, barium oxide, tin oxide. lanthanum oxide, calcium oxide, ruthenium oxide, iridium chloride, zirconium oxide, vanadium oxide, molybdenum oxide. or tungsten oxide. Catalyst Preparation The catalysts employed in the process of the present invention can be made by any conventional or suitable method known in the art including evaporation. impregnation or precipitation, each followed by calcination. In the evaporation method, the desired components are mixed together with water to form a slurry or solution. The water is evaporated and the resultant solid is then dried and calcined. This method is of value where unwanted materials are not present and a washing step is not needed. In the impregnation method, a solution of an active component or components is contacted with a support to thoroughlwet it. An excess of the impregnating solution is generally used and when the support is thoroughly saturated, the excess solution is removed, as by filtration or decantation. The impregnated support is then dried and subjected to calcination. In the precipitation method, aqueous solutions of desired constituents are mixed with a solution of a precipitating agent. A variety of bases or base-forming compounds can be used as precipitating agents, including aqueous ammonia, ammonium carbonate, ammonium bicarbonate. urea and the like. The presence of impurities in the final catalyst is minimized by carrying out the precipitation with dilute solutions and by using ammonia or ammonium salts as the precipitant along with nitrates of the desired metals. The resulting precipitate then requires a minimum of washing since any absorbed material remaining can be removed in the subsequent calcination step. In the calcination step which decomposes salts such as carbonates or nitrates to oxides, the catalyst material is heated in air to a temperature which is generally below 5000 C. The calcination is usually carried out for several hours. The process of this invention is carried out in the gas phase using well-known chemical engineering practices, which include continuous, semi-continuous, and batch operation. Preferably, the catalysts employed in the process of the present invention are activated prior to use. Activation can be achieved by preheating the catalyst at a relatively high temperature, e.g., about 3000 to 4000C. with a fluoroolefin, for a period ranging from 1 minute to 1 hour. Activation is conveniently carried out in a flow system by passing the fluoroolefin over the catalyst contained in the reactor tube. Specific fluoroolef ins suitable for use in activation of the catalyst include tetrafluoroethylene, chlorotrifluoroethene, l,l-dicbloro-2,2-difluoroethene, hexafluoropropene, perfluoro-l-butene and perfluoro-2-butene. After activation, the catalysts can be efficiently employed at at temperatures as low as about 100"C. It is not necessary that the catalyst have a high surface area. For instance, a Cr203 catalyst 2 with a surface area as low as about 5 m /g is suitable. It is preferred. however, that catalysts supported on alumina have a surface area greater than about 200 mê/g. Process Conditions Preferred reaction temperatures are about 1000 to 4000C. Pressures are about 10 3 to 10 MPa, preferably about 0.1 MPa. Contact times are preferably about 0.001 to 10 seconds. It is preferred to operate in a nonoxidative atmosphere in which molecular oxygen or similar oxidizing gases are absent. Generally. this results in fewer undesired by-products. The process is preferably carried out without any diluent but an inert atmosphere of nitrogen, helium. argon, neon, and the like can be used. Contact time of the perhaloolefins with the catalyst can vary over a wide range depending upon reaction temperature, pressure, process dynamics, and the reactants and catalysts employed. For example. in a continuous flow process, a contact time as short as about 0.001 sec can be employed. Generally, longer contact times are employed at lower temperatures. When a continuous flow process is employed, contact time is calculated using the following equation. Contact Time = Volume of Catalyst (mL) f Ga s Flow Rates (mL/hr) The transhalogenation process of the invention is conveniently carried out at atmospheric pressure, although either higher or lower pressures can be employed. The type of reactor vessel is not critical so long as it is able to withstand the temperatures and pressures employed. Corrosion resistant materials such as nickel-based corrosion resistant alloys (Hastelloy) and tantalum are preferred. The catalyst can be used in a fixed bed or a fluidized bed configuration. After the transhalogenation reaction has been completed, the reaction products can be separated by such conventional procedures as distillation. extraction by a solvent, adsorption, or other suitable techniques. Any portion of the starting perhaloolef ins that is not reacted can be recycled. EXAMPLES The following Examples illustrate the invention. All parts and percentages are by weight, and all degrees are Celsius unless otherwise noted. Preferred embodiments are represented by Examples 63 and 64. General Procedure A designated quantity of catalyst was charged to a l-cm diameter x 10-cm long glass reactor (Vycore) which was heated in a tube furnace. When indicated, the catalyst was activated by heating at an elevated temperature for a designated time in a stream of hexafluoropropene. The reactor was then cooled to the temperature selected for reaction. Flow rates of gases were measured with a mass flow controller calibrated with tetrafluoroethylene. The feeds of perhaloolef ins were started together with a feed of nitrogen if one was used. The product stream was transported directly to a gas chromatograph and analyzed on an 2.44m x 0.32cm (8' x 1/8it) column of 1% of 20M molecular weight polyethylene glycol capped with nitroterephthalic acid on activated carbon. programmed as follows: 50 for 3 min: temperature raised at 200/min to 1500: hold for 2 min; temperature raised at 350/min to 200 ; helium flow rate 20 mL/min. Product compositions are expressed in area percent with a flame ionization detector. If transhalogenation was not observed at this initial reaction temperature, the temperature was raised until reaction was observed. If conversion of perhaloolefins was complete at the initial temperature, the temperature was lowered until partial conversion was obtained. As used in the Examples, the following abbreviations for fluoroolefins and fluoroalkanes apply: FC-114; 1,2-Dichlorotetrafluoroethane; CF2ClCF2Cl FC-115: Chloropentafluoroethane; C1CF2CF3 FC-1110: Tetrachloroethene; (Cl)2C=C(Cl)2 FC-1111: Fluorotrichloroethane; F(Cl)C=C(Cl)2 FC-1112a: 1,1-Dichloro-2,2-difluoroethene; F2C=C(Cl)2 FC-1112: 1,2-Dichloro-1,2-difluorethene; F(Cl) C=C(Cl) F FC-1113: Chlorotrifluoroethene; CF(Cl)=CF2 FC-1114: Tetrafluoroethene; CF2=CF2 FC-216: 1,2-Dichlorohexafluoropropane; CF3CFClCF2Cl FC-1211: 3-Fluoropentachloro-l-propene; CFC12C(Cl)=CCl2 FC-1212: 3,3-Difluorotetrachloro-l-propene; CF2ClC(Cl)=CCl2 FC-1213: 1,1,2-Trichloro-3,3,3-trifluoro-l- propene; CF3C(Cl)=CCl2 FC-1214: 1,2-Dichloro-1,3,3,3-tetrafluoro-l- propene; CF3C(Cl)=CFCl FC-1215: 2-Chloropentafluoropropene; CF3C(Cl)=CF2 FC-1216: Hexafluoropropene; CF3CF=CF2 Catalyst Preparation Two general methods were used to prepare the catalysts used in the Examples: coevaporation and incipient wetness impregation. Method A: Coevaporation Each of the soluble inorganic salts was dissolved in water and the aqueous solutions were combined. The resulting solution was placed on a hot plate and the water was boiled off. The dry solid was then calcined in a furnace at 2000 for 1 hr, and then at 400" for 1 hr. In the preparation of the catalyst of Example 38, 10% CrF3/A1203, a solution of 73 g of hydrated aluminum nitrate, 3.7 g of hydrated chromium nitrate and 1 g of ammonium fluoride was heated to dryness, and the residue was calcined. Method B. Impregnation First, the pore volume of the support was determined by how much water could be adsorbed into its pore structure. Then, a solution of the salt to be impregnated was dissolved in this calculated amount of water, and the solid support was added. The moist supported catalyst was calcined at 100" for 1 hr, at 200" for 1 hr, and finally at 400" for 1 hr. In the preparation of the catalyst, 10% CrF3/Cr203, chromium oxide was found to adsorb 0.5 g of water/g of oxide. A solution of 0.5 g of ammonium fluoride in 2.5 mL of water was added to 5 g of Cr203. The solid catalyst was then calcined. Catalyst preparations are summarized in Table 1. All preparations were by coevaporation except where noted by (B). TABT,E 1 Catalyst Catalyst Composition Composition 10% InCl3/Al2O3 2% PdF2/Al2O3 10% CrCl3/Al2O3 18 CrF3/Cr203 2% PdCl2/Cr2O3 10% NiF2/Al2O3 20% Ce203/Al 203 9% CrF3/Cr203 20S CoCl2/Al2O3 1% NiF2/Cr203 Cr2O3 3% NiF2/Cr2O3 10% MnO/Cr2O3 9% NiF2/Cr 203 10% Al2O3/Cr2O3 10% B2O3/Al2O3 109 CoO/Cr203 20% MgCl2/Al2O3 10% Fe2O3/Cr2O3 10% P2O5/Cr2O3 10% NiO/Cr2O3 10% B203/Cr203 1% Pd/Cr203 10% CaC12/Cr203 10% CrF3/Al2O3 10% BaO/Cr2O3 10% MnF2/Al2O3 10% SnCl2/Al2O3 10% CuF2/Al2O3 10% ZnCl2/Al2O3 10% FeF3/Al2O3 10% La2O3/Al2O3 10% ZnF2/Al203 10% La2O3/Cr2O3 10% CeF3/Al2O3 10% ZrO2/Cr 203 10% CuO/Cr2O3 10% ZrO2/Al2O3 10% MnO/Cr2O3 10% CaO/Cr203 1% Pd/Cr2O3 10% Cr2O3/Al2O3-SiO2 (B) 10% CoF2/Al2O3 10% Cr2O3/TiO2-Al2O3 (B) 3% CrF3/Cr203 10% CR2O3/ZrO2 (B) 10% CrF3/Cr203 (B) Comparative Experiment In order to provide a standard against which the catalysts and processes of the present invention could be evaluated, a reaction substantially similar to those conducted as examples of the invention was conducted using AlF3 as catalyst. The AlF3 catalyst employed was a commercial catalyst marketed under the trade name Harshaw# Al-ll01. A total of 8.0 g of A1F3 catalyst was charged. and the reactor was heated to an initial temperature of 4000. Approximately equimolar streams of liquid FC-12l3, 1 mL/hr, and gaseous FC-1216, 5 mL/min, and nitrogen (10 mL/min) were started, and the products were analyzed initially on the G.C. column, as follows: FC-1216, 46%; FC-1215, 0.9%; FC-1214, 2.9%; FC-1213, 47%. Example 1 A total of 5.3.g of Cr203 catalyst (Newport Chrome) was charged, and the reactor was heated to an initial temperature of 3500. Approximately equimolar streams of liquid FC-1213, 1 mL/hr. and gaseous FC-1216, 5 mL/min, and nitrogen (20 mL/min) were started, and the products were analyzed initially on the G.C. column, as follows: FC-1216, 23S; FC-1215. 40%; FC-1214, 26%; FC-1213, 3%. The reactor temperature was lowered progressively, and transhalogenation was continued. At 900, with the same flow rates of FC-1213 and FC-1216 but with a nitrogen flow rate of 80 mL/min (calculated contact time of 0.7 sec), the product composition was 16% FC-12l6; 35% FC-1215; 9% FC-1214; 39% FC-1213. Examples 2 to 59 These Examples show a variety of catalysts which can be employed in the transhalogenation reaction: EMI14.1 FC-1216 FC-1213 FC-1214 FC-1215 The reactions were carried out by the General Procedure set forth above, with the following additional qualifications. Feed rates of 1 mL/hr of liquid FC-1213 and 5 mL/min of gaseous FC-1216 were used. Examples 2 to 4 used a nitrogen stream of 10 mL/min. and in Examples 5 to 32 and 40 to 42 a stream of nitrogen of 5 mL/min was used. No nitrogen was used in Examples 33 to 39 and 43 to 59. The catalysts used in Examples 12 to 59 were activated by pretreatment with a stream of FC-1216 (5 mL/min) at 400 for 15 min (Examples 12 to 14) or 10 min (Examples 15 to 59). The specific catalysts used. initial temperatures (tri) reaction temperatures (Ti), and product compositions are summarized in Table 2, below. TABLE 2 Product Analysis Temperature FC- FC- FC- FC Ex. catalyst. g Tj/T ( C) 1216 1215 1214 1213 2 57% MgO/AlO3, 4.7 300/400 32 20 14 32 3 19% Cr2O3/Al2O3, 7.6 400/200 17 34 23 26 4 33% Cr/Si-Al/0, 5.0 400/200 19 42 31 9 5 3% each of Ni,Co, 300/250 29 35 14 22 Fe oxides/A1203, 7.0 6 20% Fe0/A1203 300/200 39 20 4 36 7 14% NiO/Al2O3, 5.0 300/200 36 22 10 32 8 20% FeCl3/Al2O3, 5.0 300/200 24 39 26 8 9 10% MoO3/Al2O3, 5.0 300/300 47 28 16 7 10 10% WO3/Al2o3, 7.0 300/300 45 25 7 3 11 10% MnO/Al2O3, 5.8 300/200 45 14 9 30 12 10% InCl3/Al2O3, 2.5 300/200 32 24 8 31 13 0.5X Pt/AL203, 5.0 300/200 35 15 3 38 14 0.5% Pd/Al2o3 5.0 300/200 40 10 2 39 15 10% each ZnO/Cr203/ 300/200 18 34 25 11 Al2O3, 5.0 16 1% FeO/Cr2O3, 2.0 150/150 31 32 10 26 17 1% PdC12/Cr203, 2-0 150/250 44 4 11 38 18 1% Pt/Cr2O3, 2.0 150/150 41 11 4 43 19 1% CoCl2 /Cr2O3 2.0 150/150 33 5 1 61 20 20% CoCl2/Al2O3, 2.0 150/200 39 20 6 35 21 20% Ce2O3/Al2O3, 2.0 150/300 49 8 2 40 22 24% ZnO/A1203, 5.0 150/300 47 10 2 40 23 10% Ag/A1203, 2.0 150/300 45 13 8 33 24 10% CrCl3/Al2O3, 1.0 150/300 30 32 17 21 25 10% A1203/Cr203 1.0 200/300 24 31 18 23 26 10% NiO/Cr2O3, 1.0 200/200 17 42 29 12 27 10% CoO/Cr2O3, 1.0 200/200 45 12 2 4 28 10% Fe2O3/Cr2O3, 1.0 200/300 23 31 26 19 29 10%FeF3/Al2O3, 2.0 300/300 31 40 19 10 30 10% CuF/Al2O3, 2.0 300/300 51 10 3 35 31 10% ZnF2/A1203, 2.0 300/300 40 34 17 3 TABLE 2 (continued) Temperature FC- FC- FC- FC Ex. Catalyst. g T./T ( C) 1216 1215 1214 1213 32 10% CeF3SA1203, 2.0 300/300 65 20 6 5 33 10% MnF2/Al2O3, 2.0 300/300 13 26 34 21 34 10% NiF2/Al203, 2.0 300/300 19 38 29 10 35 2% PdF2/Al2O3, 2.0 300/300 33 26 17 19 36 105 CuO/Cr203, 1.0 200/300 27 46 23 4 37 10% CrF2/A1203. 2.0 300/300 63 22 3 10 38 9% CrF3/Cr2O3, 2.0 300/300 15 45 33 7 39 3% CrF3/Cr203, 2.0 300/150 18 44 21 17 40 3% NiO/Cr2O3, 1.0 200/300 16 41 28 15 41 9% NiO/Cr2O3. 1.0 200/200 12 45 36 6 42 10% CoF2/A1203, 2.0 300/300 20 41 32 6 43 10% Pbo/A1203, 2.0 300/300 25 28 21 26 44 10% Bi2O3/Al2O3, 2.0 300/300 24 29 24 22 45 10% P205/Cr203, 2.0 300/200 13 41 36 10 46 20% MgCl2/Al2O3, 2.0 300/300 47 5 1.4 45 47 10% B2O3/Al2, 2.0 300/300 47 3 2 47 48 10% B203/Cr203, 2.0 300/200 9 41 42 7 49 10% BaO/Cr203, 1.0 300/300 10 40 38 11 50 10% SnCl2/Al2O3, 3.0 300/300 47 7 3 42 51 10% ZnCl2/Al2O3, 3.0 300/300 22 41 19 17 52 10% La203/A1203, 3.0 300/300 42 14 7 36 53 10X La203/Cr2031 2.0 300/300 11 44 39 6 54 10% CaO/Cr2O3, 2.0 300/300 41 14 8 36 55 91% SiO2/Al2O3, 5.0 300/300 56 10 2 28 56 10% Cr2O3/Si-Al-O, 4.0 300/300 8 37 44 8 57 98% ZrO2/A1203, 5.0 300/300 63 4 - 28 58 Cr-Y Zeolite, 3.0 300/300 21 42 22 14 59 10% Zro2/Cr2O3, 3.0 300/400 39 12 5.4 41 Example 60 Tetrafluoroethylene + FC 1213. Reaction was carried out by the General Procedure using 5 g of the Cr203 catalyst of Example 1. 5 mL/min of gaseous tetrafluoroethylene (TFE), 0.5 mL/hr of liquid FC-1213. and 20 mL/min of nitrogen. The initial reaction temperature was 100 and the temperature was raised eventually to 2500. Reaction started at 1000. At 1500, the product composition was 23% TFE, 21% chlorotrifluoroethene, 30% FC-1215. 15% dichlorodifluorooethene, 5% FC-1214. and 3% FC-1213. Example 61 Disproportionation of Chlorotrifluoroethene. Reaction was carried out by the General Procedure using 7 g of the Cr2O3 catalyst of Example L, 5 mL/min of gaseous chlorotrifluoroethene, and 20 mL/min of nitrogen. The initial temperature was 1500. At 2500, the product composition was 8% TFE. 72t chlorotrifluoroethene, and 13% dichlorodifluoroethene. Example 62 Disproportionation of FC-1214. Reaction was carried out by the General Procedure using 8 g of the Cr2O3 catalyst of Example 1, 0.5 mL/hr of liquid FC-1214 (with cooling of the syringe), and 20 mL/min of nitrogen. The initial temperature was 100 . At 2000, the product composition was 67% FC-1214, 11 FC-1213, 21% FC-1215, and 0.6% FC-1216. Example 63 Disproportionation of FC-1215. Reaction was carried out by the General Procedure using 5 g of Cr203 catalyst, 4 mL/min of gaseous FC-1215, and 10 mL/min of nitrogen. The initial temperature was 2500. At 100 and 20 mL/min of nitrogen, the product composition was 17% FC-1216, 55t FC-12l5, 23% FC-1214, and 5% FC-1213. Example 64 Disproportionation of Chlorotrifluoroethene. Reaction was carried out by the General Procedure using 15 g of Cr203 catalyst, 5 mL/min of nitrogen. and 5 mL/min of chlorotrifluoroethene at various temperatures. The results are summarized in Table 3, below, in which the products are shown in area percent as determined by GC/MS. Disproportionation was reasonably complete at 1800 to give FC-lll4 (CF2=CF2) and FC-1112 (CF2=CC12). STABLE 3 Temp Product Analysis ( C) FC-1114 FC-115 FC-1113 FC-1112a FC-1112 FC-llll 180 17 0.8 58 9.5 11.8 1.2 200 18 1.2 56 10 12 1.4 230 15 9.9 37 20 7 3.1 250 11 18 25 28 4 5 Example 65 Disproportionation of l-Bromo-l,2,2-tri- fluoroethene. Reaction was carried out by the General Procedure using 5 g of Cr203 catalyst, 5 mL/min of gaseous l-bromo-1,2,2-trifluoroethene. and 5 mL/min of nitrogen. The initial temperature was 2500. At 3000, the product composition was shown to contain CF2=CBr2 by -nmr analysis. GC analysis of the gas stream on-line showed 3 assignable peaks: FC-1114 (9.7 area S); CF2=CFBr (32 area %); and CF2=CBr2 (32 area %). Small amounts of perhaloalkanes were seen in both the GC and NMR. Example 66 TFE + l.l-Dichloro-2.2-difluorbethene. Reaction was carried out by the General Procedure using 10 g of Cr2O3 catalyst and the designated amounts of gaseous TFE and gaseous 1,1-dichloro-2,2-difluoroerthene. The initial temperature was 275 . Reaction products are summarized in Table 4, below. TABLE 4 Feed Rate Product Analysis Temp. mL/min FC ( C) 1114 1112 1114 115 1113 114 1112 1111 275 5 5 7.1 12.2 10.6 7.7 33 5.7 275 6 4 16.5 8 9.8 9.3 29 5.3 275 4 6 14.4 5 7 7 41 8.2 300 5 5 9.6 9.4 16.3 7.2 33 6.4 250 5 5 29 2.0 11.4 3.3 44 4.3 Example 67 TFE + 1.2-Dichloro-1.2-difluoroethene. The procedure of Example 66 was employed except that 1,1-dichloro-2.2-difluoroethene was replaced with l,2-dichloro-l,2-difluoroethene (5 mL/min). The initial temperature was 275 . GC analysis showed the following principal products. Area percents are noted in parentheses: FC-1114 (26); FC-115 (9.6); FC-1113 (31); FC-114 (12.3); FC-1112 (10.6); FC-l1l1 (0.9). Example 68 FC-L216 + Tetrachloroethene. Reaction was carried out by the General Procedure using 5 g of Cr203 catalyst, activated by heating in a stream of FC-1216 (5 mL/min) at 300 for 0.5 hr. Nitrogen (5 mL/min) and liquid tetrachloroethene (5 mL/hr) streams were started. After 0.5 hr, the temperature was raised to 400 The results obtained at several temperatures are summarized in Table 5, below. TABLE 5 Temp FC-1216 FC-1215 FC-1214 FC-1112 FC-llll FC-lL10 400 24 11 3 1.4 5.3 54 400(1) 14 6.5 2.2 1.3 4.8 70 400(2) 70 13 1.6 1.6 1.8 11 300(3) 45 16 15 1.7 1.3 14.4 350(1) 22 12 4 2.7 4.2 48 (1) Tetrachloroethene flow rate was 1.5 mL/hr (2) Tetrachloroethene flow rate was 0.6 mL/hr (3) FC-1216, 10 mL/min; tetrachloroethene, 1 mL/hr Example 69 l,l-Dichloro-2,2-difluoroethene + Tetrachloroethene. Reaction was carried out by the General Procedure using 10 g of Cr203 catalyst with no activation. Nitrogen (5 ml/min), liquid tetrachloroethene (1 ml/hr), and gaseous l,1-dichloro-2,2-difluoroethene (7 to 10 ml/min) were passed over the catalyst at 3300. The principal product formed was fluorotrichloroethene. ExamPle 70 FC-1213 + Octafluoro-2-butene. Reaction was carried out by the General Procedure using 5 g of Cr203 catalyst activated by heating in a stream of gaseous octafluoro-2-butene (5 ml/min) at 4000 for 10 min. The reactor temperature was lowered to 3000, and a stream of liquid FC-1213 (1 mL/hr) was started. The temperature was lowered to 2000 and the product stream was analyzed. NMR analysis of the product showed the presence of FC-1213. FC-1214, and FC-1215 in the molar ratio of 60:21:18. Both perfluoro-cis- and perfluoro-trans-2-butene were present as well as the corresponding compounds with one or both or the vinyl fluorines replaced by chlorine. i.e. CF3CF=C(C1)CF3 and CF3C(Cl)=C(Cl)CF3. The ratio of butenes with 2:1:0 chlorine atoms was 31:29:31. Example 71 FC-1213 + Rexafluorocyclobutene. Reaction was carried out by the General Procedure using 5 g of Cr 203 catalyst, activated by heating in a stream of gaseous hexafluorocyclobutene (5 mL/min) at 4000 for 10 min. The reactor temperature was lowered to 300 , and a stream of liquid FC-1213 (1 mL/hr) was started. The reaction temperature was lowered to 200 , and a liquid sample was collected and analyzed by NMR. The following products were identified: FC-1213, FC-12L4, and FC-1215 in the molar ratio of 41:22:37; hexafluorocyclobutene, l-chloropentafluorocyclobutene, and l,2-dichlorotetrafluorocyclobutene in the molar ratio of 8:39:54. Example 72 FC-12L3 + Octafluorocyclopentene. Reaction was carried out by the General Procedure using 5 g of Cr203 catalyst, activated by heating in a stream of gaseous octafluorocyclopentene (5 mL/min) at 4000 for 10 min. The reactor temperature was lowered to 3000, and a stream of liquid FC-1213 (1 mL/hr) was started. The reaction product was analyzed by fluorine nmr. The following products were identified: equimolar amounts of FC-1213, FC-1214, and FC-1215; equimolar amounts of octafluorocyclopentene. l-chloroheptafluorocyclopentene, and 1.2-dichlorohexafluorocyclopentene. Example 73 FC-1213 + Perfluoro-4-methyl-2-pentene. Reaction was carried out by the General Procedure using 5 g of Cr203 catalyst, activated by heating in a stream of gaseous FC-1216 (5 mL/min) and nitrogen (5 mL/min) at 4000 for 10 min. The reactor temperature was lowered to 3000 and the FC-1216 stream was discontinued. A stream of liquid (1 mL/hr) consisting of an equimolar mixture of FC-1213 and perfluoro-4-methyl-2-pentene was started. GC/MS showed the presence of 4 isomers of C6FllCl and NMR showed the presence of FC-1213, FC-1214. and FC-1215 in the molar ratio of 12:5:1.

Claims: CLAIMS 1. A process for preparing fluoroolefins of the formula: R1R2C=CR3R8 and R5R6C=CR7R4 which comprises reacting at from 100 to 400 0C at a contact time of from 0.001 to 10 seconds a perhaloolefin of the formula: RlR2C=CR3R4 with a perhaloolefin of the formula: R 5R6 C=CR7R8 in the presence of a solid catalyst, as charged to the reactor, selected from: : A. chromium oxide alone or in combination with one or more of Rh , Ru , Ir , Pd , Pt , Ag , phosphorous oxide, silicon oxide, boron oxide or an oxide or halide of aluminum, manganese, zinc, iron, rhodiumn, nickel, palladium, cobalt, platinum, cerium, silver, copper, lead, bismuth, iridium, magnesium, barium, tin, lanthanum, calcium, ruthenium, iridium, zirconium, vanadium, molybdenum, or tungsten; and B. aluminum oxide in combination with one or more of Rh , Ru , Ir , Pd , Pt , Ag , Silicon oxide, phosphorous oxide, boron oxide or an oxide or halide of manganese, zinc, iron, rhodium, nickel, palladium, cobalt, platinum, cerium, silver, copper, lead, bismuth, iridium, magnesium, barium, tin, lanthanum, calcium, ruthenium, iridium, zirconium, vanadium, molybdenum, or tungsten; wherein R1, R21 R3, R5, R6 and R7 are independently selected from F, Cl, Br, C1 to C4 perfluoroalkyl and pentafluorophenyl; or RÚ and R together, Rê and R together, R5 and R7 together or R6 and R7 together, when both groups are in the cis configuration, may also represent perfluoroalkylene of 2 to 4 carbons or o-C6F4(-)CF2-; R8=F; R4=Cl or Br; none of the fluoroolefins simultaneously contain both C1 and Br; and R1, R2, R3, R4, R51 R6 and R7 may be chosen as to product identical structures for the reactants or for the products. 2. A process according to Claim 1 wherein the catalyst is unsupported Cr2O3. 3. A process according to Claim 1 wherein the catalyst is Cr2O3 supported on alumina. 4. A process according to Claim 1 wherein the catalyst is MnO supported on alumina. 5. A process according to any one of the preceding claims wherein one of the products is a perfluoroolefin containing 2 to 10 carbon atoms. 6. A process according to any one of the preceding claims wherein the perhaloolefin reactants have 2 or 3 carbon atoms. 7. A process according to any one of the preceding claims comprising disproportionating one reactant.

Inventors: WEIGERT, FRANK JULIAN
Applicants: E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1986
Main classification: C07C17
IPC codes: C07C17