Method for producing fluoroolefin compound

Abstract

To provide a method for producing a fluoroolefin compound having four or more carbon atoms, in an industrially inexpensive manner, with a high conversion rate and high selectivity.SOLUTION: The present invention provides a method for producing a fluoroolefin compound having four or more carbon atoms, the method having a step of subjecting a halogenated fluoroolefin compound having two or more carbon atoms to dimerization, in the presence of an alkali metal fluoride, to obtain the fluoroolefin compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a process for producing a fluoroolefin compound. [Background technology]

[0002] Fluoroolefin compounds with 4 or more carbon atoms, such as hexafluoro-2-butene, are In general, specific three-membered ring-containing fluorine-containing compounds are produced in the presence of an aluminum chlorofluoride (ACF) catalyst. or reacting tetrafluoroethylene with CF3CF2I. (For example, see Non-Patent Document 1). [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Journal of Fluorine Chemistry 102 (2000) 199-204. Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure relates to a method for producing fluoroolefin compounds having 4 or more carbon atoms at high conversion and low cost industrially. The object of the present invention is to provide a method for producing tertiary amine with high selectivity. [Means for solving the problem]

[0005] The present disclosure encompasses the following configurations.

[0006] Item 1. A method for producing a fluoroolefin compound having 4 or more carbon atoms, comprising: In the presence of an alkali metal fluoride, A halogenated fluoroolefin compound having two or more carbon atoms is dimerized to produce said fluoro Obtaining an olefin compound A manufacturing method comprising:

[0007] Item 2. The fluoroolefin compound is represented by the general formula (1): CF3CR=CRCF3(1) [In the formula, R represents a fluorine atom or a fluoroalkyl group.] Item 3. The method according to item 1, wherein the fluoroolefin compound is represented by the formula:

[0008] Item 3. The fluoroolefin compound is represented by the general formula (1A):

[0009] [ka] [In the formula, each R represents a fluorine atom or a fluoroalkyl group.] Item 3. The method according to item 1 or 2, wherein the fluoroolefin compound is represented by the formula:

[0010] Item 4. The halogenated fluoroolefin compound is represented by the general formula (2): CF2=CRX (2) [In the formula, R represents a fluorine atom or a fluoroalkyl group, and X represents a halogen atom other than a fluorine atom.] 4. The method according to any one of items 1 to 3, wherein the fluoroolefin compound is represented by the formula:

[0011] Item 5. The halogenated fluoroolefin compound is represented by the general formula (2A):

[0012] [ka] [In the formula, R represents a fluorine atom or a fluorine-containing alkyl group, and X represents a halogen atom other than a fluorine atom.] 5. The method according to any one of items 1 to 4, wherein the halogenated fluoroolefin compound is represented by the formula:

[0013] Item 6. The specific surface area of ​​the alkali metal fluoride is 500 to 2000 m2 / g, any of items 1 to 5 3. The method for producing a semiconductor device according to claim 1,

[0014] Item 7. The method according to any one of Items 1 to 6, wherein the alkali metal fluoride is supported on a carrier.

[0015] Item 8. The production method according to Item 7, wherein the content of the alkali metal fluoride is 0.1 to 75 mass%, based on 100 mass% of the total amount of the support and the alkali metal fluoride.

[0016] Item 9. The method according to any one of Items 1 to 8, wherein the dimerization reaction is carried out in the presence of a fluorine-containing gas.

[0017] Item 10. The production method according to any one of Items 1 to 9, wherein in the dimerization reaction, a contact time (W / F) of the halogenated fluoroolefin compound to the alkali metal fluoride (total amount of the support and the alkali metal fluoride when the halogenated fluoroolefin compound is supported on a support) is 5 to 200 g sec / cc.

[0018] Item 11. The method according to any one of Items 1 to 10, wherein the dimerization reaction is carried out at a reaction temperature of 200 to 500° C.

[0019] Section 12. General formula (1A):

[0020] [ka] [In the formula, each R represents a fluorine atom or a fluoroalkyl group.] and a fluoroolefin compound represented by the formula: General formula (3):

[0021] [ka] [In the formula, R is the same as above.] and a fluoroolefin compound represented by the formula:

[0022] Item 13. The composition according to item 12, which is used as a cleaning gas or an etching gas. Effect of the Invention

[0023] According to the present disclosure, it is possible to industrially and inexpensively produce fluoroolefin compounds having 4 or more carbon atoms. It is possible to obtain the product with high conversion and high selectivity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] In this specification, "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of." In addition, in this specification, when a numerical range is shown as "A to B," it means A or more and B or less.

[0025] In the present disclosure, "selectivity" means the ratio (mol %) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the total molar amount of compounds other than the raw material compound in the effluent gas.

[0026] In the present disclosure, the term "conversion rate" means the ratio (mol %) of the total molar amount of compounds other than the raw material compounds contained in the effluent gas from the reactor outlet to the molar amount of the raw material compounds supplied to the reactor.

[0027] In the present disclosure, the term "yield" refers to the ratio (mol %) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the molar amount of the raw material compounds supplied to the reactor.

[0028] 1. Method for producing fluoroolefin compounds The method for producing a fluoroolefin compound disclosed herein comprises dimerizing a halogenated fluoroolefin compound having two or more carbon atoms in the presence of an alkali metal fluoride to produce the fluoroolefin compound. The process includes a step of obtaining an olefin compound.

[0029] Conventionally, fluoroolefins with 4 or more carbon atoms, such as hexafluoro-2-butene, have been used. As a method for synthesizing the compound, for example, a method in the presence of an aluminum chlorofluoride (ACF) catalyst is used. It has been known that a specific three-membered ring-containing fluorine compound can be subjected to a ring-opening reaction under the conditions described above. However, in this method, it is difficult to industrially obtain the three-membered ring-containing fluorine compound, which is the raw material compound, and therefore it is difficult to produce fluoroolefin compounds having 4 or more carbon atoms on an industrial level. In addition, it is difficult to synthesize fluoroolefin compounds having 4 or more carbon atoms. can be prepared, for example, by reacting tetrafluoroethylene with tetrafluoroethylene in the presence of an aluminum chlorofluoride (ACF) catalyst. It is also known to react ethylene with CF3CF2I (Non-Patent Document 1). However, in this method, the raw material compound CF3CF2I is expensive and Therefore, both methods are difficult to carry out on an industrial scale for mass production.

[0030] According to the present disclosure, as described above, in the presence of an alkali metal fluoride, By subjecting a halogenated fluoroolefin compound to a dimerization reaction, a fluoroolefin compound having 4 or more carbon atoms can be industrially produced at low cost with high conversion and high selectivity.

[0031] (1-1) Halogenated fluoroolefin compounds The halogenated fluoroolefin compound that can be used as a raw material compound in the production method of the present disclosure is a halogenated fluoroolefin compound having 2 or more carbon atoms. The carbon number of the fluoroolefin compound is 4 or more, which is industrially available and inexpensive. From the viewpoint of obtaining a fluoroolefin compound with a higher conversion rate and a higher selectivity, 12 is preferable, and 2 to 8 is more preferable.

[0032] As the halogenated fluoroolefin compound, from the viewpoint of industrially producing a fluoroolefin compound at low cost, particularly with a high conversion, yield and selectivity, a halogenated fluoroolefin compound represented by the general formula (2): CF2=CRX (2) [In the formula, R represents a fluorine atom or a fluoroalkyl group, and X represents a halogen atom other than a fluorine atom.] Preferred are halogenated fluoroolefin compounds represented by the general formula (2A):

[0033] [ka] [In the formula, R represents a fluorine atom or a fluorine-containing alkyl group, and X represents a halogen atom other than a fluorine atom.] More preferred are halogenated fluoroolefin compounds represented by the following formula:

[0034] In the general formula (2), examples of the fluorine-containing alkyl group represented by R include fluorine-containing alkyl groups having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as a trifluoromethyl group and a pentafluoroethyl group. (particularly perfluoroalkyl groups).

[0035] In the general formula (2), examples of the halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom.

[0036] As for the halogenated fluoroolefin compound as the raw material compound, from the viewpoint of industrially obtaining a fluoroolefin compound at a higher conversion rate and higher selectivity at a lower cost, R is preferably a fluorine atom or a perfluoroalkyl group (particularly a fluorine atom), and X is preferably a chlorine atom.

[0037] Specific examples of halogenated fluoroolefin compounds as raw material compounds that satisfy the above conditions include:

[0038] [ka] These halogenated fluoroolefin compounds can be used alone or in combination of two or more. The compound may be a known or commercially available product.

[0039] (1-2) Dimerization reaction In the step of dimerizing a halogenated fluoroolefin compound in the present disclosure, for example, the halogenated fluoroolefin compound is a halogenated fluoroolefin represented by general formula (2): In the case of a fluoroolefin compound, X is eliminated to give a halogenated fluoroolefin. In other words, the halogenated fluoroolefin compound, which is the raw material compound, can be subjected to a condensation reaction through dehalogenation to obtain the target fluoroolefin compound.

[0040] For example, in the case of a halogenated fluoroolefin compound represented by the general formula (2A) as a raw material compound, R is preferably a fluorine atom and X is preferably a chlorine atom.

[0041] That is, the reaction is as follows:

[0042] [ka] Therefore, fluoroolefin compounds (hexafluoro-2-butene, etc.) can be produced industrially and inexpensively. It is preferable to obtain high conversion and high selectivity.

[0043] (1-3) Alkali metal fluorides The step of dimerizing the halogenated fluoroolefin compound in the present disclosure is carried out in the presence of an alkali metal fluoride. The alkali metal fluoride functions as a catalyst and can produce the fluoroolefin compound with particularly high conversion, yield and selectivity.

[0044] The alkali metal fluoride is not particularly limited, but from the viewpoint of producing a fluoroolefin compound with a particularly high conversion rate, yield and selectivity, the fourth alkali metal fluoride is preferably used. Fluorides of alkali metals of the seventh period are preferred, for example, potassium fluoride (KF), Cesium fluoride (CsF) is more preferable. These alkali metal fluorides are not used alone. It is also possible to use two or more of them in combination.

[0045] The specific surface area of ​​the alkali metal fluoride is preferably 500 to 2000 m from the viewpoint of producing a fluoroolefin compound with a particularly high conversion rate, yield, and selectivity. 2 / g is preferable, and 800 to 1500m 2 In the present disclosure, the specific surface area of ​​the alkali metal fluoride is measured by the BET method. When the specific surface area of ​​the alkali metal fluoride is within this range, the density of the alkali metal fluoride particles is not too small, so that the target compound can be obtained with a higher selectivity. It is also possible to further improve the conversion rate of the raw material compound. As described later, even when the alkali metal fluoride is supported on a carrier, there is no significant difference in the specific surface area, and the specific surface area when the alkali metal fluoride is supported on a carrier is preferably within the above range.

[0046] In the present disclosure, when the reaction is carried out in a gas phase, the above-mentioned raw material compound is contacted with an alkali metal fluoride. In this case, from the viewpoint of reactivity, it is preferable to contact the alkali metal fluoride in a solid state (solid phase).

[0047] In the present disclosure, for example, when a gas-phase continuous flow reaction is carried out, from the viewpoint of reactivity, The potassium metal fluoride may be in the form of a powder, but is preferably in the form of pellets. The above-mentioned alkali metal fluoride may be used as it is, but may be supported on a carrier. This improves the reaction efficiency of the alkali metal fluoride, and the fluoroolefin compound can be produced with a particularly high conversion rate, yield, and selectivity. The carrier to be supported is not particularly limited, and examples thereof include carbon, alumina, zirconia, silica, titania, zeolite, silica alumina, and chromium oxide. Examples of carbon include activated carbon, amorphous carbon, graphite, and diamond. These carriers may be used alone, or may be used in combination with two carriers. Of these, carbon is preferred, and activated carbon is more preferred, from the viewpoints of its large specific surface area and ease of supporting an alkali metal fluoride.

[0048] When the alkali metal fluoride is supported on a carrier, the amount of the supported alkali metal fluoride is not particularly limited, but from the viewpoint of being able to produce a fluoroolefin compound with particularly high conversion, yield and selectivity, the amount of the alkali metal fluoride supported is preferably 0.1 to 75 mass%, and more preferably 1 to 60 mass%, of 100 mass% in total of the carrier and the alkali metal fluoride.

[0049] The bulk density of the alkali metal fluoride supported on the carrier is preferably 0.01 to 10 g / mL, more preferably 0.1 to 5 g / mL, from the viewpoint of producing a fluoroolefin compound with particularly high conversion, yield and selectivity. In the present disclosure, the bulk density of the alkali metal fluoride supported on the carrier is measured by a bulk density measuring device. When the bulk density of the alkali metal fluoride supported on the carrier is within such a range, the density of the particles of the alkali metal fluoride supported on the carrier is not too small, so that the target compound can be obtained with a higher selectivity. In addition, it is also possible to further improve the conversion rate of the raw material compound.

[0050] The pore volume of the alkali metal fluoride supported on the carrier is preferably 0.1 to 1.5 mL / g, more preferably 0.25 to 1.0 mL / g, from the viewpoint of producing a fluoroolefin compound with particularly high conversion, yield and selectivity. The pore volume of the fluoride is measured by the BET method. When the pore volume is within this range, the density of the alkali metal fluoride particles supported on the carrier is not too small, so that the target compound can be obtained with higher selectivity. In addition, it is also possible to further improve the conversion rate of the raw material compound.

[0051] The average pore diameter of the alkali metal fluoride supported on the carrier is preferably 5 to 20 μm, more preferably 8 to 15 μm, from the viewpoint of producing a fluoroolefin compound with particularly high conversion, yield and selectivity. In the present disclosure, the average pore diameter of the alkali metal fluoride supported on the carrier is measured by the BET method.

[0052] (1-4) Fluorine-containing gases The above-mentioned alkali metal fluoride also functions as a catalyst, and can produce fluoroolefin compounds with particularly high conversion, yield and selectivity.However, the alkali metal fluoride contains fluorine atoms, and fluorine atoms can be extracted during the reaction to obtain fluoroolefin compounds.Therefore, the amount of alkali metal fluoride that effectively functions as a catalyst may decrease as the reaction proceeds for a long time.Therefore, in order to replenish fluorine atoms, it is preferable to carry out the above-mentioned dimerization reaction in the presence of a gas containing fluorine.

[0053] There is no particular limitation on such a fluorine-containing gas, and examples thereof include F2, HF, and CFCl3. , CF2Cl2, CFHCl2, CF2HCl, CF3H, NF3, IF5, IF7, FCl, ClF3, etc.

[0054] In the present disclosure, when the reaction is carried out in a gas phase, the above-mentioned fluorine-containing gas is preferably used in a gaseous state (gas phase).

[0055] (1-5) Reaction temperature In the step of obtaining a fluoroolefin compound by subjecting a halogenated fluoroolefin compound to a dimerization reaction (condensation reaction by dehalogenation) in the present disclosure, the reaction temperature is usually preferably 200 to 500°C, more preferably 250 to 450°C, and even more preferably 300 to 400°C, from the viewpoint of producing the fluoroolefin compound with particularly high conversion, yield, and selectivity.

[0056] (1-6)Reaction time In the present disclosure, when a reaction is carried out in a gas phase, for example, when a gas phase flow system is adopted, the reaction time is the contact time (W / F) of the raw material compound (halogenated fluoroolefin compound) with the catalyst (alkali metal fluoride; if supported on a carrier, the total amount of carrier and alkali metal fluoride) [W: catalyst (alkali metal fluoride; if supported on a carrier, the total amount of carrier and alkali metal fluoride] The reaction conversion rate is particularly high and the fluoroolefin compound is more efficiently produced. From the viewpoint of obtaining a higher yield and a higher selectivity, the contact time is preferably 5 to 200 g·sec. / cc, more preferably 10 to 150 g·sec. / cc, and even more preferably 15 to 100 g·sec. / cc. The contact time means the time during which the raw material compound and the catalyst are in contact with each other.

[0057] The above contact times indicate conditions when the reaction is carried out in the gas phase, particularly in a gas phase continuous flow system, but can also be appropriately adjusted when the reaction is carried out in a batch system.

[0058] In the present disclosure, when the dimerization reaction is carried out in the presence of a fluorine-containing gas, the content of the fluorine-containing gas is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, and even more preferably 1 to 2.5 mol, per mol of the raw material compound (halogenated fluoroolefin compound), from the viewpoint of particularly high conversion rate of the reaction and capable of producing a fluoroolefin compound in higher yield and higher selectivity.

[0059] (1-7) Reaction pressure In the present disclosure, the reaction pressure when obtaining a fluoroolefin compound by dimerization reaction (condensation reaction by dehalogenation) of a halogenated fluoroolefin compound is preferably -0.05 to 2 MPa, more preferably -0.01 to 1 MPa, and even more preferably normal pressure to 0.5 MPa, from the viewpoint of producing the fluoroolefin compound with particularly high conversion, yield and selectivity. In the present disclosure, the pressure is a gauge pressure unless otherwise specified.

[0060] In the reaction of the present disclosure, the reactor in which the raw material compound (halogenated fluoroolefin compound) is reacted in the presence of an alkali metal fluoride and, if necessary, a gas containing fluorine is present, is not particularly limited in shape and structure as long as it can withstand the above-mentioned temperature and pressure. Examples of the reactor include a vertical reactor, a horizontal reactor, and a multi-tube reactor. Examples of the material of the reactor include glass, stainless steel, iron, nickel, and iron-nickel alloy.

[0061] (1-8) Reaction example The step of obtaining a fluoroolefin compound by subjecting a halogenated fluoroolefin compound to a dimerization reaction (condensation reaction by dehalogenation) in the present disclosure can be carried out by either a continuous gas-phase flow method or a batch method in which a raw material compound (halogenated fluoroolefin compound) is continuously charged into a reactor and a target compound (fluoroolefin compound) is continuously withdrawn from the reactor. If the target compound remains in the reactor, a polymerization reaction of the halogenated fluoroolefin compound may occur, resulting in the production of a polymer, so it is preferable to carry out the step by a continuous gas-phase flow method. The step of obtaining a fluoroolefin compound by subjecting a halogenated fluoroolefin compound to a dimerization reaction (condensation reaction by dehalogenation) in the present disclosure. In the case of the continuous gas phase reaction, it is preferable to carry out the reaction in a gas phase, and in particular to carry out the reaction in a continuous gas phase flow system using a fixed bed reactor. In the case of carrying out the reaction in a continuous gas phase flow system, the apparatus and operation can be simplified and it is economically advantageous.

[0062] In the present disclosure, the step of dimerizing a halogenated fluoroolefin compound (condensation reaction by dehalogenation) to obtain a fluoroolefin compound is preferably carried out under an inert gas atmosphere from the viewpoint of suppressing deterioration of an alkali metal fluoride. Examples of the inert gas include nitrogen, helium, and argon. Among these inert gases, nitrogen is preferred from the viewpoint of reducing costs. The concentration of the inert gas is preferably 0 to 50 mol% of the gas components introduced into the reactor. When the dimerization reaction is carried out in the presence of a fluorine-containing gas, the dimerization reaction can be carried out under an atmosphere of the fluorine-containing gas or a mixed atmosphere of the inert gas and the fluorine-containing gas. The concentration of the fluorine-containing gas is preferably 0.1 to 90 mol% of the gas components introduced into the reactor.

[0063] After completion of the reaction, purification treatment can be carried out according to a conventional method, if necessary, to obtain a fluoroolefin compound.

[0064] (1-9) Target compound The target compound of the present disclosure thus obtained is a fluoroolefin having 4 or more carbon atoms. Compounds (particularly perfluoroolefin compounds having 4 or more carbon atoms), for example, compounds represented by the general formula (1): CF3CR=CRCF3(1) [In the formula, R represents a fluorine atom or a fluoroalkyl group.] The fluoroolefin compound may include both cis and trans isomers, but the trans isomer is preferred from the viewpoint of production with high conversion, yield and selectivity, and is represented by the general formula (1A):

[0065] [ka] [In the formula, each R represents a fluorine atom or a fluoroalkyl group.] Preferred is a fluoroolefin compound represented by the following formula:

[0066] R in the general formula (1) is the same as R in the above-mentioned general formula (2). In addition, in order to dimerize the above-mentioned raw material compound, a fluoroolefin compound in which two R are the same is used. Therefore, the fluoroolefin represented by the general formula (1) to be produced is easily produced. Specific examples of the phenyl compound include:

[0067] [ka] etc.

[0068] As described above, the fluoroolefin compound obtained in the present disclosure may be a cis isomer or a trans isomer. In addition, the fluoroolefin compound may be a mixture of a cis isomer and a trans isomer. In the case of a mixture of cis and trans isomers, the mixture may be used as is or may be isolated in a conventional manner before use.

[0069] The fluoroolefin compounds thus obtained can be effectively used in various applications, such as etching gases and cleaning gases for forming cutting-edge fine structures in semiconductors, liquid crystals, and the like.

[0070] 2. Composition In the manner described above, a fluoroolefin compound can be obtained, but it may also be obtained in the form of a composition containing the fluoroolefin compound.

[0071] For example, the general formula (1A):

[0072] [ka] [In the formula, each R represents a fluorine atom or a fluoroalkyl group.] and a fluoroolefin compound represented by the formula: General formula (3):

[0073] [ka] [In the formula, R is the same as above.] and a fluoroolefin compound represented by the formula:

[0074] In the general formulae (1A) and (3), R can be as defined above.

[0075] In this case, the total amount of the composition of the present disclosure is taken as 100 mol %, and A The content of the fluoroolefin compound represented by general formula (3) is preferably 95.0 to 99.9 mol %, and more preferably 98.0 to 99.5 mol %. The content of the fluoroolefin compound represented by general formula (4) is preferably 0.1 to 4.0 mol %, and more preferably 0.5 to 1.5 mol %, based on 100 mol % of the total amount of the composition of the present disclosure.

[0076] The composition also has the general formula (4): CF3CFRX (4) [In the formula, R and X are the same as above.] and compounds represented by the general formula (5): CF3CFHR (5) [In the formula, R is the same as above.] The compound may also include a compound represented by the formula:

[0077] In this case, the total amount of the composition of the present disclosure is taken as 100 mol %, and the compound represented by the general formula (4) The content is preferably 0.01 to 1.00 mol %, more preferably 0.05 to 0.50 mol %. In addition, the content of the compound represented by the general formula (5) is 0.01 to 0.20 mol %, based on the total amount of the composition of the present disclosure being 100 mol %. % by mole, and more preferably 0.02 to 0.10 mol %.

[0078] According to the production method of the present disclosure, even when the above-mentioned composition is obtained, the fluoroolefin compound represented by general formula (1A) can be obtained industrially and inexpensively with a high reaction conversion rate, in high yield and with high selectivity. Therefore, it is possible to reduce the amount of components other than the fluoroolefin compound represented by general formula (1A) in the composition. This makes it possible to reduce the purification effort required to obtain the fluoroolefin compound represented by general formula (1A).

[0079] Such compositions of the present disclosure can be effectively used in various applications, such as etching gases and cleaning gases for forming cutting-edge fine structures in semiconductors, liquid crystals, and the like.

[0080] Although the embodiment of the present disclosure has been described above, various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0081] The following examples will clarify the features of the present disclosure, but the present disclosure is not limited to these examples.

[0082] Synthesis example 1: 50% CsF / AC Activated carbon (specific surface area 1200m 2 / g) and cesium fluoride were mixed so that the amount of cesium fluoride used was 50% by mass, with the total amount of activated carbon and cesium fluoride being 100% by mass, and the activated carbon was A 50% CsF / AC catalyst supported by cesium fluoride was obtained. The specific surface area of ​​the obtained catalyst was 600 m 2 / g, pore volume was 0.7 mL / g, and pore diameter was 10 μm.

[0083] Synthesis example 2: 5% CsF / AC Activated carbon (specific surface area 1200m 2 The activated carbon was mixed with cesium fluoride in an amount of 5% by mass, with the total amount of activated carbon and cesium fluoride being 100% by mass, to obtain a 5% CsF / AC catalyst in which cesium fluoride is supported on activated carbon. The specific surface area of ​​the obtained catalyst was 900 m 2 / g, pore size The volume was 0.8 mL / g and the pore size was 10 μm.

[0084] Synthesis example 3: 5%KF / AC Activated carbon (specific surface area 1200m 2 The activated carbon was mixed with potassium fluoride in an amount of 5% by mass, with the total amount of activated carbon and potassium fluoride being 100% by mass, to obtain a 5% KF / AC catalyst in which cesium fluoride is supported on activated carbon. The specific surface area of ​​the obtained catalyst was 900 m 2 / g, pore volume was 0.8 mL / g, and pore diameter was 10 μm.

[0085] Examples 1 to 5 In the methods for producing fluoroolefin compounds in Examples 1 to 5, the raw material compound is a compound represented by the general formula (2): In the halogenated fluoroolefin compound represented by the formula: 1 is a fluorine atom, and X is a chlorine atom. The reaction is as follows:

[0086] [ka] According to the procedure described above, a fluoroolefin compound (hexafluoro-2-butene) was obtained.

[0087] 10 g of the catalyst obtained in Synthesis Example 1, 2 or 3 was added to a reaction tube (SUS pipe with an outer diameter of 1 / 2 inch). After drying for 2 hours at 200°C under a nitrogen atmosphere, CF2=CFCl was added to the reaction tube at normal pressure so that the contact time (W / F) between CF2=CFCl (raw material compound) and the catalyst was 15g·sec / cc or 30g·sec / cc. (Raw material compound) was distributed.

[0088] The reaction was carried out in a continuous gas phase flow mode.

[0089] The reaction tube was heated to 300° C. to initiate the reaction.

[0090] One hour after the start of the reaction, the distillate that had passed through the removal tower was collected.

[0091] Then, gas chromatography (Shimadzu Corporation, product name "GC-2014") was used. Mass analysis was performed using gas chromatography / mass spectrometry (GC / MS), and NMR (JEOL Structural analysis was carried out by NMR spectroscopy using a tertiary amine compound (manufactured by Epson Corporation, trade name "400YH").

[0092] The results of mass spectrometry and structural analysis confirmed that the target compound, CF3CF=CFCF3, was produced. The conditions of catalyst, temperature and contact time, as well as the results, are shown in Table 1.

[0093] [Table 1]

Claims

1. General formula (1A): 【Chemistry 1】 [In the formula, each R represents a fluorine atom or a fluoroalkyl group.] and a fluoroolefin compound represented by the formula: General formula (3): 【Chemistry 2】 [In the formula, R is the same as above.] A composition comprising a fluoroolefin compound represented by the formula: A composition, wherein the content of the fluoroolefin compound represented by the general formula (1A) is 95.0 to 99.9 mol % relative to the total amount of the composition being 100 mol %.

2. The composition described in claim 1, wherein the content of the fluoroolefin compound represented by the general formula (3) is 0.1 to 4.0 mol %, with the total amount of the composition being 100 mol %.

3. Further, the general formula (4): CF3CFRX (4) [In the formula, R is the same as above. X represents a halogen atom other than a fluorine atom.] The composition according to claim 1 or 2, comprising a compound represented by the formula:

4. The composition described in claim 3, wherein the content of the fluoroolefin compound represented by the general formula (4) is 0.01 to 1.00 mol %, with the total amount of the composition being 100 mol %.

5. Further, the general formula (5): CF3CFHR (4) [In the formula, R is the same as above.] The composition according to any one of claims 1 to 4, comprising a compound represented by the formula:

6. The composition described in claim 5, wherein the content of the compound represented by the general formula (5) is 0.01 to 0.20 mol %, with the total amount of the composition being 100 mol %.

7. The composition according to any one of claims 1 to 6, which is used as a cleaning gas or an etching gas.

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