WO1995006022A1 - Procede de production d'hexafluorocyclobutene et procede de production d'hexafluorocyclobutane - Google Patents
Procede de production d'hexafluorocyclobutene et procede de production d'hexafluorocyclobutane Download PDFInfo
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- WO1995006022A1 WO1995006022A1 PCT/JP1994/001285 JP9401285W WO9506022A1 WO 1995006022 A1 WO1995006022 A1 WO 1995006022A1 JP 9401285 W JP9401285 W JP 9401285W WO 9506022 A1 WO9506022 A1 WO 9506022A1
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- reaction
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- hexafluorocyclobutene
- hydrogen
- hexafluorocyclobutane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
- C07C23/02—Monocyclic halogenated hydrocarbons
- C07C23/06—Monocyclic halogenated hydrocarbons with a four-membered ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
- C07C17/281—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons of only one compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
Definitions
- the present invention is a useful compound that can be used not only as a raw material for HFC blowing agents and detergents that do not destroy the ozone layer, but also as a raw material for various resins or an intermediate for medical and agricultural chemicals.
- (Z) — 1,2,3,3,4,4-1 is a useful compound that can be a substitute for CFC and HCFC used as a method for producing cyclobutene, and as a refrigerant, blowing agent, and washing agent. Hexafluorosix It relates to the git method of ⁇ -butane.
- the reaction for obtaining hexafluorocyclo ⁇ -butene from 1,2-dicyclohexafluorocyclobutane is a reaction with zinc in alcohol CG. Fuller and JC Tatlow, J. Chem. Soc, 3198 (1961)] Etc. are known.
- (Z) — 1,2,3,3,4,4-hexafluro ⁇ -cycloptane 3 ⁇ 4ii method is to prepare 1,2-diclohexafluorocyclobutane with lithium aluminum hydride (LiA The method of reducing with 1 H 4 ) (the above-mentioned literature) is known.
- An object of the present invention is to provide a method for easily deriving 1,2-dichlorohexafluorocyclobutane, which is available at a low cost, into hexafluorocyclobutene with high selectivity.
- Another object of the present invention is to provide a process for reducing hexafluorocyclobutene by
- An object of the present invention is to provide a method for obtaining high yields of xafluorocyclobutane.
- Still another object of the present invention is to provide (Z) —1,2,3,3,4,4 xafluoro-cyclobutane with 1,2-diclohexafluorohexyl ⁇ -butane hydrogen (Z) — 1, 2, 3, 3,
- the present inventors have conducted intensive studies on an efficient and inexpensive process for producing hexafluorocyclobutene, and as a result, have found that 1,2-dic ⁇ -hexafluorocyclobutane, which can be obtained from ⁇ i, has a high selectivity.
- the inventors have often found a process for deriving hexafluorocyclobutene, and have completed the present invention.
- the present invention provides a method for desalting 1,2-dichlorohexafluorocyclobutane with hydrogen in the presence of a catalyst comprising a metal oxide and a metal oxide or a metal oxide.
- the present invention relates to the ⁇ i method of hexafluorocyclobutene.
- the raw material 1,2-dichlorohexafluorocyclobutane can be easily obtained by dimerization of 1,2,2-trifluoro-1-alk ⁇ ethylene.
- Metal oxides used as catalysts in the reductive dehalogenation (dechlorination) of 1,2-dicyclohexafluorocyclobutane include Cr, Fe,
- An aqueous ammonia solution or alkali metal hydroxide is added to an aqueous solution of chlorides, sulfates or nitrates of Co, Cu, Ni and Mn by a general method, and the precipitated metal hydroxide is added. It is obtained by firing.
- These can be used alone, but a composite oxide or a mixed oxide of a plurality of metals selected from these metals can also be used for the reaction. These may be granulated or may be IB! Into pellets. Further, these may be supported on a carrier that does not directly participate in the reaction, for example, a carrier composed of at least one of activated carbon, alumina, aluminum fluoride, calcium fluoride and the like. These metal oxides may be reduced to zero during pretreatment with hydrogen or during the reaction, and may become zero-valent.
- oxide of gayne used for the catalyst commercially available granular, spherical, or powdered silicon dioxide can be used.
- CARI ACT manufactured by Fuji Devison Co., Ltd. Si 1 bead manufactured by Mizusawa Chemical Industry Co., Ltd.
- MS GELSIL manufactured by Asahi Glass Co., Ltd. are pulverized or pelletized according to JOE ⁇ . You may use it.
- the reaction can be carried out if the excess ratio of hydrogen is at least 1 mole (at least stoichiometric amount) of the raw materials required for the reaction, but practically 1.5 moles or more. It is preferred to do so. In addition, excess hydrogen reduces the reaction time by shortening the contact time, so that it is practically used at about 2 to 5 moles.
- the reaction temperature in the reductive de-Nono halogenated is suitably selected depending on the activity of the catalyst in the range of 200 to 500 e C. As is generally known, increasing the reaction temperature increases the reaction rate, so that a low activity and a high reaction rate are required when a catalyst is used. However, if it exceeds 500, the proportion of the linear or C2 compound, which is considered to have a carbon-carbon bond cleaved, tends to increase and the selectivity tends to decrease.
- the contact time can be appropriately selected according to the catalytic activity and the conversion rate desired in the reaction. Generally, when the catalytic activity is low, the contact time can be extended to set an appropriate conversion.
- the present inventor has also conducted intensive studies on a method for producing (Z) -1,2,3,3,4,4-hexafluorocyclobutane. As a result, the use of hexafluorocyclobutene as a raw material, It has been found that the target product can be obtained with high selectivity by performing hydrogen reduction below, leading to completion of the present invention.
- the system of the gas phase reaction may be a system such as a fixed bed type gas phase reaction or a fluidized bed type gas phase reaction. This may be the same in the above-described method for producing hexafluorocyclobutene according to the present invention.
- the palladium catalyst used is activated carbon, alumina, silica gel, and titanium oxide. Those supported on a carrier comprising at least one selected from tan and zirconia are preferred.
- the particle size of the carrier has little effect on the reaction, but is preferably from 0.1 to: lOOmra, and the carrier concentration can be as wide as 0.05 to 10%. Usually, 0.5 to 5% supported products are recommended (these may also be employed in the above-described method for producing hexafluorocyclobutene according to the present invention).
- the reaction is usually carried out at 20-300, preferably 50 to 150 e C.
- the ratio of hydrogen to raw material can vary greatly, and at least a stoichiometric amount of hydrogen can be used.
- hydrogenation is usually carried out using 2 to 5 times the stoichiometric amount of hydrogen.
- Significantly greater than stoichiometric amounts, for example 10 moles or more, of hydrogen can be used, based on the total moles of starting material.
- the pressure of the reaction is not particularly limited, and the reaction can be performed under increased pressure, reduced pressure, or normal pressure.However, since the apparatus becomes complicated under reduced pressure, it is preferable to perform the reaction under increased pressure or normal pressure. Is usually 0.1 to 300 seconds, particularly 1 to 30 seconds (these may also be employed in the above-described method for hexafluorocyclobutene of the present invention).
- hexafluorocyclobutene as a raw material is prepared by the above-mentioned method (that is, 1,2,3,3,3,4,4).
- a catalyst comprising a metal oxide and an oxide of ⁇ or gayne.
- 1,2-dichloromouth hexafluorocyclobutane used for producing this hexafluorocyclobutene is converted to 1,2,2-trifluorofluorene. It can be obtained by dimerization of ethylene.
- the present inventor further studied the method for producing (Z) -l, 2,3,3,4,4-hexafluorocyclobutane.
- 1,2-dicyclohexafluorocyclobutane was used as a raw material.
- hydrogen reduction was carried out in the presence of a rhodium catalyst, the desired product could be obtained with high yield and low selectivity, and completed the present invention.
- (E) -1,2,3,3,4,4-hexafluorocyclobutane which is a geometric isomer of the target product was not formed.
- the gist of the present invention is that a 1,2-dichlorohexafluorocyclobutane is used as a raw material, and hydrogen is used in an amount of at least 2 equivalents to the raw material.
- hydrogenation reaction By carrying out the hydrogenation reaction at a temperature of 300, there is a method of producing (Z) —1,2,3,3,4,4-hexafluorocyclobutane in high yield.
- a rhodium catalyst when used according to the present invention, the conversion of the raw material is very high, and the conversion to the geometric isomer (E) —1, 2, 3, 3, 4, 41 Little or no xafluorocyclobutane is formed, and the target product is (Z) — 1, 2, 3, 3, 4, 4 Hexafluorocyclobutane is obtained with high selectivity. It became clear that it could be done.
- a carrier for the catalyst it is possible to use a carrier composed of at least one kind selected from activated carbon, alumina, silica, zirconia, etc., which is generally known. Activated carbon is most preferable, and high selectivity of a desired product can be obtained.
- Activated carbon is most preferable, and high selectivity of a desired product can be obtained.
- a method of the gas phase reaction a method such as a fixed bed type gas phase reaction and a fluidized bed type gas phase reaction can be employed.
- the particle size of the carrier has little effect on the reaction, but is preferably in the range of 0.1 to 10%.
- the loading concentration a wide range of 0.05 to 10% can be used, but a loading of 0.5 to 5% is usually used.
- Reaction ia3 ⁇ 4 is usually 150-300, preferably 175-250. 150.
- the selectivity is high, but the conversion is apt to decrease, and the reaction ia e exceeding 3 oo e c produces a large amount of by-products.
- the ratio of hydrogen to the raw material is such that the hydrogen is stoichiometric or more with respect to the 1,2-diclohexafluorocyclobutane.
- hydrogenation is usually carried out using 2 to 10 times, in particular 2 to 4 times, the stoichiometric amount of hydrogen.
- stoichiometric amounts for example 10 moles or more, of hydrogen can be used, based on the total moles of starting material. Excess hydrogen can be recovered and reused.
- the pressure of the reaction is not particularly limited, and the reaction can be performed under increased pressure, reduced pressure, or normal pressure. However, since the apparatus becomes complicated under reduced pressure, it is preferable to perform the reaction under increased pressure or normal pressure.
- the contact time is usually 0.1-300 seconds, especially 1-30 seconds.
- 1,2-Dichrohexafluorosiloxane the raw material for this hydrogen reduction reaction Lobutane is obtained by applying 1,2,2-trifluoro-monochloropiethylene under pressure (especially at a pressure of 2 kg / cm 2 or more, and a gaseous phase 2 at a pressure of 200 to 400 ⁇ 3 ⁇ 4). It can be synthesized by a quantification reaction.
- the higher the pressure of this dimerization reaction the higher the conversion at a lower temperature and the more selective the desired 1,2-dichlorohexafluorocyclobutane can be obtained.
- the reaction pressure is made higher, a high pressure-resistant reactor is required as the reaction apparatus. Therefore, the reaction is usually preferably performed at 2 to 20 kg / cm 2 .
- 1,2-dichlorohexafluorocyclobutane is dechlorinated with hydrogen in the presence of a catalyst comprising a metal oxide and an oxide of Z or gayne to form a hexane.
- Fluorocyclobutene is manufactured.
- ⁇ Available 1,2-dichrohexafluorocyclobutane can be easily derived to hexafluorocyclobutene in one step with high selectivity. .
- This hexafluorocyclobutene can be used not only as an HFC foaming agent and a raw material for washing that does not destroy the ozone layer, but also as a raw material for various resins or pharmaceutical and agricultural chemicals. It is a useful compound that can also be an intermediate.
- (Z) — 1,2,3,3,4,4-hexafluorocyclobutane is produced by hydrogen reduction of hexafluorocyclobutene by a gas phase method in the presence of a palladium catalyst. ⁇ The target product can be obtained with the selectivity.
- This (Z) —1,2,3,3,4,4-hexafluorocyclobutane is a useful compound that can be a substitute for CFC and HCFC used as a refrigerant and ⁇ m detergent.
- the Cr (N0 3) 3 ⁇ 9H 2 0 of 120g was dissolved in water of 250 ml, with stirring and an aqueous solution 200 of hydroxide Anmoniumu this and 28, the hydroxide is added to water heated 4 100 ml A precipitate was obtained. This was separated by filtration, washed with 7j, and dried, and then calcined at 450 for 5 hours to obtain an oxide (chromium oxide) powder. This was molded into a cylinder with a diameter of 5 mra and a height of 5 mm using a tableting machine.
- Hastelloy C reaction tube (O20ramx 1000 mm) was filled with 10 g of the above-described ⁇ -oxide catalyst, and this was reacted.
- Pretreatment was performed by preliminarily flowing hydrogen at 200 / min for 3 hours. Thereafter, 1,2-dicyclohexafluorocyclobutane was flowed at 50 ⁇ / min.
- the main by-product was tetrafluoro-1-chlorobutane, but the desired hexafluorocyclobutene (1,2,3,3,4,4-hexafluoro-1-cyclobutene) reacted well. It can be seen that the composition can be performed at the rate and the selectivity.
- Example 2 The reaction was carried out in the same manner as in Example 1 except that the acid ( ⁇ -one-mia complex oxide was used as a catalyst.
- the results are shown in Table 2 below, and the target hexafluorocyclobutene was It can be seen that it can be synthesized with good reaction rate and high selectivity.
- the main by-product was tetrafluoro-1-chlorocyclobutene, but it can be seen that the desired hexafluorocyclobutene can be synthesized with good conversion and high selectivity.
- 3 ⁇ 4H reaction tube ( ⁇ 20 ⁇ X1000) was filled with 10 g of the above-obtained nickel oxide gel catalyst (silica gel carrier), and this was set for the reaction. Pretreatment was carried out by previously flowing 7j element for 20 hours (k nin for 3 hours.) Then, 1,2-dichrohexafluorocyclobuta
- the main by-product was tetrafluoro-1-chlorocyclobutene, but it can be seen that the desired hexafluorocyclobutene can be synthesized with good conversion and high selectivity.
- the 120g C r (NO s) 8 ⁇ 9 H 2 0 was dissolved in 250 ⁇ of water and dried by adding thereto shea Rikageru 181 g. This was heated to 400 to obtain chromium oxide. This was molded into a cylinder with a diameter of 5 mm and a height of 5 mm using a tablet molding machine. A reaction tube made of Hastelloy C ( ⁇ 20 ⁇ 1000 tubes) was filled with 10 g of the above-obtained chromium oxide catalyst (the carrier was silica gel), and the reaction temperature was set. Hydrogen in advance Pretreatment was performed by flowing for 3 hours. Thereafter, 1,2-dichlorohexafluorocyclobutane was flowed at 50 / min.
- the main by-product was tetrafluoro-1-chlorocyclobutene, but it can be seen that the desired hexafluorocyclobutene can be synthesized with good conversion and high selectivity.
- the main by-product was tetrafluoro-1-chlorocyclobutene, but it can be seen that the desired hexafluoro ⁇ -cyclobutene can be synthesized with good conversion and selectivity.
- Hastelloy C3 ⁇ 4M tube ( ⁇ 20 xiOOOmra) was filled with 10 g of CARiACT-30 (manufactured by Fuji Devison Co., Ltd.) and heated at 400 for 3 hours while nitrogen was applied to the thigh at 40 cc / min.
- Example 7 the starting material was hydrogen at 30 cc / min, 1,2-dichlorohexafluorocyclobutane was 3 cc / min, and the reaction temperature was 450.
- Example 7 the catalyst was changed to Silbead (manufactured by Mizusawa Chemical Industry Co., Ltd.), and the same procedure was followed.
- Example 10 The same reactor as in Example 10 was charged with 4.6 cc of a palladium catalyst supported on activated carbon at a concentration of 3%, and heated to 80 in an electric furnace while flowing nitrogen gas to reach a predetermined temperature. Thereafter, hexafluorocyclobutene was introduced at a rate of 8 ccZ, and hydrogen was introduced at a rate of 40 ccZ. The reaction temperature was kept at 80.
- Example 10 The same reactor as in Example 10 was filled with 2.3 cc of a palladium catalyst supported on activated carbon at a concentration of 0.5%, and after flowing nitrogen gas at room temperature, hexafluorocyclobutene was added in an amount of 5 ccZ, and 7J element was added in a lOccZ. Minutes introduced. The reaction temperature was kept at 27.
- Example 10 The same reactor as in Example 10 was charged with 1.9 cc of a palladium catalyst supported on alumina at a concentration of 0.5%, and heated to 100 ° C. in an electric furnace while flowing nitrogen gas to reach a predetermined temperature. Thereafter, hexafluorocyclobutene was introduced at a rate of 5 cc / minute and hydrogen was introduced at a rate of 15 cc / minute. The reaction temperature was kept at 100. The generated gas was washed with water and analyzed by gas chromatography. The results are shown in Table 7 below. Table 7
- the main by-product was tetrafluoro-1-chlorocyclo ⁇ -butene, but the desired ( ⁇ ) — 1,2,3,3,4,4 1-hexafluorocyclobutane was highly reactive. It can be seen that synthesis can be performed at the selectivity.
- Example 14 In the same reaction apparatus as in Example 14, was charged a supported mouth Jiumu catalyst 1 g of 3% concentration on active carbon, while passing nitrogen gas, heated in an electric furnace to 225 e C, after a predetermined of , 1,2-Dichlorohexafluoro ⁇ -cyclobutane and hydrogen 10. Reaction 225. C kept. The generated gas is analyzed by gas chromatography after washing with water. I got it. The results are shown in Table 8 below.
- Example 14 The same reactor as in Example 14 was charged with 1 g of a rhodium catalyst supported on activated carbon at a concentration of 3%, and heated to 250 in an electric furnace while flowing nitrogen gas to reach a predetermined i3 ⁇ 4g. , 1,2-Di- ⁇ -hexafluorosiloxane ⁇ -butane was introduced at a rate of 1.5 minutes, and hydrogen was introduced at a rate of 10 minutes. The reaction remained at 250. The generated gas was analyzed by gas chromatography after 7i washing. The results are shown in Table 8 below.
- Example 14 The same reactor as in Example 14 was charged with 1 g of a rhodium catalyst supported on activated carbon at a concentration of 3%, and heated to 150 in an electric furnace while flowing nitrogen gas. 1,2-Dicyclohexacyclobutane was introduced at a rate of 1 min, and hydrogen was introduced at a rate of 10.0 ⁇ / min. Reaction 150 remained at 150. The generated gas was analyzed by gas chromatography after washing with water. The results are shown in Table 8 below.
- Example 14 The same reactor as in Example 14 was charged with 1 g of a palladium catalyst supported on activated carbon at a concentration of 0.5%, and heated to 200 in a m furnace while flowing nitrogen gas to reach a predetermined temperature. Thereafter, 1,2-dichlorohexafluorocyclobutane was introduced at a rate of 1.7 mS / min, and 7j element was introduced at a rate of 10 minutes. The reaction was kept at 200. The generated gas was analyzed by gas chromatography after washing with water. The results are shown in Table 8 below.
- Example 14 The same reactor as in Example 14 was charged with 1 g of a white medium supported on activated carbon at a concentration of 0.5%, and heated to 150 in an electric furnace while flowing nitrogen gas. After reaching the specified ia ⁇ , 1,2-diclohexafluorocyclobutane was introduced at a rate of 1.4 mi / min and hydrogen was introduced at a rate of 10. min. The reaction was kept at 150. The generated gas was analyzed by gas chromatography after washing by 7 jc. The results are shown in Table 8 below.
- the desired (Z) —1,2,3,3,4,4-hexafluorocyclobutane can be obtained with a high selectivity, and the desired reaction can be performed depending on the reaction temperature. It can be seen that the ratio can be obtained.
- Example 18 The same apparatus as in Example 18 was filled with glass beads 20J ⁇ having a diameter of about Iran, and while flowing nitrogen gas, the internal pressure of the reaction tube was adjusted to 2 kg / cra 2 by a reverse pressure control valve, and the pressure was reduced to 400 at Italy. After the mixture was heated and reached a predetermined temperature, trifluoroethylene styrene was introduced at a rate of 1 minute. The reaction temperature was kept at 400. The generated gas was analyzed by gas chromatography. The results are shown in Table 9 below.
- Example 18 The same apparatus as in Example 18 was charged with nickel beads 2 (about 2 mm in diameter) filled with ki, and while flowing nitrogen gas, the internal pressure of the reaction tube was adjusted to 4 kg / cm 2 with a reverse pressure control valve, and 350 mm in a mm furnace. After heating to ° C and reaching the specified temperature, trifluoroethylene was added at a rate of 75 ⁇ / min. The reaction SJ ⁇ was maintained at 350. The product gas was analyzed by gas chromatography. The results are shown in Table 9 below.
- Example 18 The same apparatus as in Example 18 was charged with 3 ⁇ spherical spherical silica gel (CAR i ACT), and while flowing nitrogen gas, the internal pressure of the reaction tube was adjusted to 4 kg / cm 2 with a reverse pressure control valve. Te was heated to 350 e C, after reaching the predetermined temperature, was introduced click port ⁇ triflate Ruo Russia ethylene at a rate of min. Reaction iS g was kept at 350. The generated gas was analyzed by gas chromatography. The results are shown in Table 9 below.
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Description
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/600,920 US5763703A (en) | 1993-08-27 | 1994-08-03 | Manufacturing method for hexafluorocylobutene and hexafluorocyclobutane |
DE69419516T DE69419516T2 (de) | 1993-08-27 | 1994-08-03 | Verfahren zur herstellung von hexafluorocyclobuten und verfahren zur herstellung von hexafluorocyclobutan |
EP94923068A EP0716065B1 (en) | 1993-08-27 | 1994-08-03 | Process for producing hexafluorocyclobutene and process for producing hexafluorocyclobutane |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP5/235531 | 1993-08-27 | ||
JP23553193 | 1993-08-27 | ||
JP6/12209 | 1994-01-10 | ||
JP01220994A JP3500617B2 (ja) | 1993-08-27 | 1994-01-10 | ヘキサフルオロシクロブタンの製造方法 |
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WO1995006022A1 true WO1995006022A1 (fr) | 1995-03-02 |
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PCT/JP1994/001285 WO1995006022A1 (fr) | 1993-08-27 | 1994-08-03 | Procede de production d'hexafluorocyclobutene et procede de production d'hexafluorocyclobutane |
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US (1) | US5763703A (ja) |
EP (2) | EP0881202B1 (ja) |
JP (1) | JP3500617B2 (ja) |
DE (2) | DE69419516T2 (ja) |
WO (1) | WO1995006022A1 (ja) |
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JP3729281B2 (ja) * | 1994-11-24 | 2005-12-21 | 独立行政法人産業技術総合研究所 | 弗素化アルケン誘導体および弗素化アルカン誘導体の製造方法 |
RU2264376C1 (ru) * | 2004-06-15 | 2005-11-20 | Закрытое акционерное общество АСТОР ЭЛЕКТРОНИКС | Способ получения гексафторбутадиена и 1,2- дихлоргексафторциклобутана |
CN102947255B (zh) | 2010-06-23 | 2016-04-06 | 旭硝子株式会社 | 2,3,3,3-四氟丙烯的制造方法 |
CA3123450A1 (en) | 2018-12-21 | 2020-06-25 | Honeywell International, Inc. | Heat transfer methods, systems and fluids |
CN113646289A (zh) * | 2019-03-27 | 2021-11-12 | 大金工业株式会社 | 卤代环烷烃化合物的制造方法 |
CN110981688B (zh) * | 2019-10-31 | 2021-03-23 | 中国矿业大学(北京) | 一种气相催化合成3,4,4-三氟环丁烯的方法 |
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JPH01132538A (ja) * | 1987-11-17 | 1989-05-25 | Asahi Glass Co Ltd | テトラフルオロエタンの製造方法 |
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DE856145C (de) * | 1943-03-12 | 1952-11-20 | Hoechst Ag | Verfahren zur Herstellung von Fluor und Chlor enthaltenden Kohlenwasserstoffen |
US2436142A (en) * | 1943-09-03 | 1948-02-17 | Du Pont | Polyfluorocyclobutenes |
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NL292631A (ja) * | 1962-05-14 | |||
US3996299A (en) * | 1973-02-08 | 1976-12-07 | Phillips Petroleum Company | Fluoro compound preparation |
DE3735467A1 (de) * | 1987-10-20 | 1989-05-03 | Bayer Ag | Verfahren zur herstellung von fluorierten c(pfeil abwaerts)4(pfeil abwaerts)- bis c(pfeil abwaerts)6(pfeil abwaerts)-kohlenwasserstoffen und neue cyclische fluorierte kohlenwasserstoffe, sowie die verwendung von fluorierten c(pfeil abwaerts)4(pfeil abwaerts)- bis c(pfeil abwaerts)6(pfeil abwaerts)-kohlenwasserstoffen als treibgas und arbeitsfluessigkeit fuer waermepumpensysteme |
US5068473A (en) * | 1989-02-03 | 1991-11-26 | E. I. Du Pont De Nemours And Company | Hydrogenolysis/dehydrohalogenation process |
EP0449977B1 (en) * | 1989-02-03 | 1994-06-15 | E.I. Du Pont De Nemours And Company | Improved hydrogenolysis/dehydrohalogenation process |
US5136113A (en) * | 1991-07-23 | 1992-08-04 | E. I. Du Pont De Nemours And Company | Catalytic hydrogenolysis |
JPH05124987A (ja) * | 1991-11-01 | 1993-05-21 | Daikin Ind Ltd | 1,1,1,2,2,4,4,4−オクタフルオロブタンの製造方法 |
ES2104790T3 (es) * | 1991-11-01 | 1997-10-16 | Solvay | Procedimiento para la preparacion de 1,1,1,2,3,3,3-heptafluoropropano (r227). |
JP3275338B2 (ja) * | 1992-01-13 | 2002-04-15 | ダイキン工業株式会社 | 1,1,1,4,4,4−ヘキサフルオロブタンの製造方法 |
DE4214739A1 (de) * | 1992-05-04 | 1993-11-11 | Bayer Ag | Verfahren zur Herstellung von Hexafluorchlorbutenen |
RU94046237A (ru) * | 1992-06-05 | 1996-10-27 | Дайкин Индастриз Лтд. (JP) | Способы производства 1,1,1,2,3-пентафторпропилена и способы производства 1,1,1,2,3-пентафторпропана |
JPH0687771A (ja) * | 1992-09-04 | 1994-03-29 | Daikin Ind Ltd | 1,1,1,2,3−ペンタフルオロプロパンの製造方法 |
JP3369604B2 (ja) * | 1992-09-04 | 2003-01-20 | ダイキン工業株式会社 | 1,1,1,2,3,3−ヘキサフルオロプロパンの製造方法及びテトラフルオロクロロプロペンの製造方法 |
JP3407379B2 (ja) * | 1993-06-10 | 2003-05-19 | ダイキン工業株式会社 | 1,1,1,3,3−ペンタフルオロプロパンの製造方法 |
US5416246A (en) * | 1994-10-14 | 1995-05-16 | E. I. Du Pont De Nemours And Company | Chlorofluorocarbon isomerization |
-
1994
- 1994-01-10 JP JP01220994A patent/JP3500617B2/ja not_active Expired - Fee Related
- 1994-08-03 WO PCT/JP1994/001285 patent/WO1995006022A1/ja active IP Right Grant
- 1994-08-03 EP EP98114189A patent/EP0881202B1/en not_active Expired - Lifetime
- 1994-08-03 EP EP94923068A patent/EP0716065B1/en not_active Expired - Lifetime
- 1994-08-03 DE DE69419516T patent/DE69419516T2/de not_active Expired - Fee Related
- 1994-08-03 US US08/600,920 patent/US5763703A/en not_active Expired - Fee Related
- 1994-08-03 DE DE69430146T patent/DE69430146T2/de not_active Expired - Fee Related
Patent Citations (2)
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US3636173A (en) * | 1969-07-28 | 1972-01-18 | Phillips Petroleum Co | Hydrodehalogenation process and catalyst |
JPH01132538A (ja) * | 1987-11-17 | 1989-05-25 | Asahi Glass Co Ltd | テトラフルオロエタンの製造方法 |
Non-Patent Citations (3)
Title |
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CHEMICAL ABSTRACTS, Vol. 106, No. 23, 8 June 1987 (08.06.87), (Columbus, Ohio, USA), S.M. IVANOVA AND ANOTHER: "Kinetics of dimerization of chlorotrifluoroethylene", Refer to page 674, Abstract No. 195666j, KINET, KATAL. 1986, 27(5), 1236-7 (Russ). * |
CHEMICAL ABSTRACTS, Vol. 71, No. 1, 7 July 1969 (07.07.69), (Columbus, Ohio, USA), LIONEL HILAIRE AND ANOTHER: "Catalytic hydrogenation of hexafluorocyclobutene", Refer to page 273, Abstract No. 3020h, & BULL. SOC. CHIM. FR. 1969, (3), 842-7 (Fr). * |
See also references of EP0716065A4 * |
Also Published As
Publication number | Publication date |
---|---|
JPH07112944A (ja) | 1995-05-02 |
DE69419516D1 (de) | 1999-08-19 |
DE69430146D1 (de) | 2002-04-18 |
EP0881202B1 (en) | 2002-03-13 |
JP3500617B2 (ja) | 2004-02-23 |
EP0716065B1 (en) | 1999-07-14 |
EP0716065A4 (en) | 1996-11-20 |
DE69419516T2 (de) | 2000-02-03 |
US5763703A (en) | 1998-06-09 |
DE69430146T2 (de) | 2002-11-07 |
EP0716065A1 (en) | 1996-06-12 |
EP0881202A1 (en) | 1998-12-02 |
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