Halogenated butene compositions

Abstract

The present invention provides a composition containing a halogenated butene compound represented by general formula (1) and a halogenated butane compound represented by general formula (3), the content of the halogenated butene compound represented by general formula (1) being 91.00-99.99 mol% with respect to 100 mol% of the total amount of the composition: general formula (1): CX1X2X3CX4 = CHCX7X8X9 (1) [wherein X1, X2, X3, X4, X7, X8 and X9 are the same or different and represent halogen atoms. ] General Formula (3): CX1X2X3CX4X5CHX6CX7X8X9 (3) [In the formula, X1, X2, X3, X4, X7, X8, and X9 are the same as described above. And one of X5 and X6 represents a hydrogen atom and the other represents a halogen atom. ].

Description

[0001] This case is a divisional application of a patent application with an application date of February 14, 2020 and an application number of 202080015744.4 (PCT / JP2020 / 005856) and an invention title of "Method for Producing Halogenated Butene Compound". Technical Field

[0002] The present invention relates to a method for producing a halogenated butene compound. Background Art

[0003] Butene compounds having 7 halogen atoms, represented by heptafluorobutene, are compounds highly anticipated as dry etching gases for semiconductors, cleaning gases, building blocks for organic synthesis, and the like.

[0004] As a method for producing the butene compound having 7 halogen atoms, for example, in Non-Patent Document 1, after reacting CF3C≡CCF3 with AgF to obtain CF3CF═C(CF3)Ag, it is reacted with HCl in acetonitrile to obtain CF3CF═CHCF3.

[0005] Prior Art Documents

[0006] Non-Patent Documents

[0007] Non-Patent Document 1: Journal of the American Chemical Society, 91, 1969, p. 6532 - 6534 Summary of the Invention

[0008] Technical Problem to be Solved by the Invention

[0009] An object of the present invention is to provide a method with high conversion rate and capable of obtaining a butene compound having 7 halogen atoms with high selectivity.

[0010] Technical Solution for Solving the Technical Problem

[0011] The present invention includes the following solutions.

[0012] Item 1. A method for producing a halogenated butene compound represented by the general formula (1), which includes a step of reacting a halogenated butyne compound of the general formula (2) with a hydrogen halide in the presence of a catalyst,

[0013] General formula (1):

[0014] CX 1 X 2 X 3 CX 4 =CHCX 7 X 8 X 9 (1)

[0015] [In the formula, X 1 , X 2 , X 3 , X 4 , X 7 , X 8 and X 9 are the same or different and represent a halogen atom.]

[0016] General formula (2):

[0017] CX 1 X 2 X 3 C≡CCX 7 X 8 X 9 (2)

[0018] [In the formula, X 1 , X 2 , X 3 , X 7 , X 8 and X 9 are the same as those described above.].

[0019] Item 2. The production method according to Item 1, wherein the butene halide compound represented by the general formula (1) is CF3CF=CHCF3, and the butyne halide compound represented by the general formula (2) is CF3C≡CCF3.

[0020] Item 3. The production method according to Item 1 or 2, wherein the catalyst contains at least one selected from a fluorinated or non-fluorinated activated carbon catalyst and a fluorinated or non-fluorinated Lewis acid catalyst.

[0021] Item 4. The production method according to any one of Items 1 to 3, wherein the catalyst is a fluorinated or non-fluorinated Lewis acid catalyst, and the Lewis acid catalyst is at least one selected from a chromium oxide catalyst, an alumina catalyst, a silica-alumina catalyst, and a zeolite catalyst.

[0022] Item 5. The production method according to any one of Items 1 to 4, wherein 30 to 250 moles of hydrogen halide are reacted with respect to 1 mole of the butyne halide compound represented by the general formula (2).

[0023] Item 6. A composition containing a butene halide compound represented by the general formula (1) and a butane halide compound represented by the general formula (3),

[0024] assuming that the total amount of the composition is 100 mol%, the content of the butene halide compound represented by the general formula (1) is 91.00 to 99.99 mol%,

[0025] General formula (1):

[0026] CX 1 X 2 X 3 CX 4 =CHCX 7 X 8 X 9 (1)

[0027] [In the formula, X 1 , X 2 , X 3 , X 4 , X 7 , X 8 and X 9 are the same or different and represent halogen atoms.]

[0028] General formula (3):

[0029] CX 1 X 2 X 3 CX 4 X 5 CHX 6 CX 7 X 8 X 9 (3)

[0030] [In the formula, X 1 , X 2 , X 3 , X 4 , X 7 , X 8 and X 9 are the same as those above. One of X 5 and X 6 represents a hydrogen atom and the other represents a halogen atom.].

[0031] Item 7. The composition according to Item 6, which is used as a cleaning gas, an etching gas, or a building block for organic synthesis.

[0032] Effects of the Invention

[0033] According to the present invention, a butene compound having 7 halogen atoms can be synthesized by a method capable of obtaining a product with a high conversion rate and a high selectivity. Detailed Description of the Invention

[0034] In this specification, "containing" is a concept including any one of "comprise", "consist essentially of", and "consist of". Also, in this specification, when a numerical range is expressed as "A to B", it means A or more and B or less.

[0035] In the present invention, the "selection rate" 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 total molar amount of the compounds other than the raw material compound in the effluent gas.

[0036] In the present invention, the "conversion rate" refers to the ratio (mol%) of the total molar amount of the compounds other than the raw material compound contained in the effluent gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

[0037] Currently, according to the method of Non-Patent Document 1, after reacting CF3C≡CCF3 with AgF to obtain CF3CF═C(CF3)Ag, it is reacted with HCl in acetonitrile to obtain CF3CF═CHCF3. However, two steps of reaction are required, and the total yield is only 57%.

[0038] Thus, with the existing method, the reaction has a yield of only 57% and a large number of steps. By using the production method of the present invention, compared with the existing method, a butene compound having 7 halogen atoms can be synthesized by a method with a high conversion rate and a high selection rate to obtain the product.

[0039] 1. Method for producing halogenated butene compound

[0040] The method for producing a halogenated butene compound of the present invention is a method for producing a halogenated butene compound represented by the general formula (1), and includes a step of reacting a halogenated butyne compound of the general formula (2) with hydrogen halide in the presence of a catalyst.

[0041] General formula (1):

[0042] CX 1 X 2 X 3 CX 4 =CHCX 7 X 8 X 9 (1)

[0043] [In the formula, X 1 , X 2 , X 3 , X 4 , X 7 , X 8 and X 9 are the same or different and represent halogen atoms.]

[0044] General formula (2):

[0045] CX 1 X 2 X 3 C≡CCX 7 X8 X 9 (2)

[0046] [wherein X 1 、X 2 、X 3 、X 7 、X 8 and X 9 are the same as those described above.].

[0047] In the production method of the present invention, if the reaction of the butynyl halide compound represented by the general formula (2) with hydrogen halide is carried out without a catalyst, a butane halide compound represented by the general formula (3) in which 2 moles of hydrogen halide are added to 1 mole of the butynyl halide compound represented by the general formula (2) is formed as a by-product to a considerable extent (for example, in an amount more than 9.00 mol%).

[0048] General formula (3):

[0049] CX 1 X 2 X 3 CX 4 X 5 CHX 6 CX 7 X 8 X 9 (3)

[0050] [wherein X 1 、X 2 、X 3 、X 4 、X 7 、X 8 and X 9 are the same as those described above. One of X 5 and X 6 represents a hydrogen atom, and the other represents a halogen atom.].

[0051] On the other hand, by carrying out the reaction of the butynyl halide compound represented by the general formula (2) with hydrogen halide in the presence of a catalyst, it is possible to suppress the addition of 2 moles of hydrogen halide to 1 mole of the butynyl halide compound represented by the general formula (2), and it is possible to selectively obtain a butenyl halide compound represented by the general formula (1) in which 1 mole of hydrogen halide is added to 1 mole of the butynyl halide compound represented by the general formula (2). This is because the trihalomethyl group (CX 1 X 2 X 3 and CX 7 X 8 X 9)It has the effect of a strong electron-withdrawing group. Due to this strong electron-withdrawing effect, the methyl trihalide reduces the electron density of the adjacent double bond and triple bond. Therefore, the addition reaction to this unsaturated bond is not likely to occur. The butynyl halide compound has a triple bond and high reactivity, so it easily undergoes an addition reaction with hydrogen halide. However, due to the effect of the methyl trihalide, the butenyl halide compound does not react with hydrogen halide and does not form a butane halide compound, and a butenyl halide compound can be selectively obtained.

[0052] As described above, the butynyl halide compound that can be used as a substrate in the production method of the present invention is the butynyl halide compound represented by the general formula (2),

[0053] General formula (2):

[0054] CX 1 X 2 X 3 C≡CCX 7 X 8 X 9 (2)

[0055] [In the formula, X 1 , X 2 , X 3 , X 7 , X 8 and X 9 are the same or different and represent halogen atoms.].

[0056] In the general formula (2), as the halogen atoms represented by X 1 , X 2 , X 3 , X 7 , X 8 and X 9 , fluorine atom, chlorine atom, bromine atom and iodine atom can be cited.

[0057] As the butynyl halide compound as a substrate, particularly from the viewpoint of being able to produce a butenyl halide compound with high conversion rate, yield and selectivity, it is preferred that X 1 , X 2 , X 3 , X 7 , X 8 and X 9 are all fluorine atoms.

[0058] The above-mentioned X 1 , X 2 , X 3 , X 7 , X 8 and X 9 can be the same or different respectively.

[0059] As the butyne halide compound serving as the substrate satisfying the above conditions, specifically, CF3C≡CCF3, CCl3C≡CCCl3, CBr3C≡CCBr3, etc. can be cited. These butyne halide compounds can be used alone or in combination of two or more. Such butyne halide compounds can be those known in the art or commercially available products. In addition, they can also be synthesized according to the usual methods such as those disclosed in Japanese Patent Application Laid-Open No. 2012-001448.

[0060] As the hydrogen halide that reacts with the butyne halide compound, hydrogen fluoride, hydrogen chloride, hydrogen bromide, etc. can be cited. In addition, from the viewpoints of reaction conversion rate, yield, and selectivity, hydrogen fluoride is preferred. These hydrogen halides can be used alone or in combination of two or more.

[0061] The hydrogen halide is usually preferably supplied to the reactor in a gaseous state together with the butyne halide compound (substrate). The supply amount of the hydrogen halide that reacts with the butyne halide compound (substrate) is preferably 30 to 250 moles, more preferably 35 to 240 moles, and even more preferably 40 to 230 moles relative to 1 mole of the butyne halide compound (substrate). By setting it within this range, the addition reaction of the hydrogen halide can proceed better, and the excessive addition reaction of the hydrogen halide can be further suppressed. As a result, the generation of impurities can be further reduced, the selectivity of the resulting butene halide compound is high, and it can be recovered in a high yield.

[0062] In the present invention, the step of reacting the butyne halide compound with the hydrogen halide is an addition reaction of the hydrogen halide and is carried out in the presence of a catalyst. The step (addition reaction) of reacting the butyne halide compound with the hydrogen halide in the production method of the present invention is preferably carried out in a gaseous phase, particularly in a continuous gas flow type using a fixed-bed reactor. When carried out in a continuous gas flow type in the gaseous phase, the apparatus, operation, etc. can be simplified, and it is economically advantageous.

[0063] In the step of reacting the butyne halide compound with the hydrogen halide in the present invention, for example, among the butyne halide compounds represented by the general formula (2) as the substrate, X 1 、X 2 、X 3 、X 7 、X 8 and X 9 are more preferably fluorine atoms.

[0064] That is, preferably, according to the following reaction formula, it is an addition reaction of hydrogen fluoride.

[0065] CF3C≡CCF3 + HF → CF3CF=CHCF3

[0066] As the catalyst used in the production method of the present invention, a fluorinated or non-fluorinated activated carbon catalyst, a fluorinated or non-fluorinated Lewis acid catalyst, etc. are preferred.

[0067] As the activated carbon catalyst, there is no particular limitation, and powdered activated carbons such as crushed carbon, formed carbon, granular carbon, and spherical carbon can be cited. The powdered activated carbon is preferably a powdered activated carbon having a particle size shown as 4 mesh (4.75 mm) to 100 mesh (0.150 mm) in the JIS test (JIS Z8801). These activated carbons can be publicly known or commercially available products.

[0068] The activated carbon exhibits stronger activity through fluorination. Therefore, fluorinated activated carbon obtained by previously fluorinating the activated carbon before use in the reaction can also be used. That is, as the activated carbon catalyst, either unfluorinated activated carbon or fluorinated activated carbon can be used.

[0069] As the fluorinating agent for fluorinating the activated carbon, for example, in addition to inorganic fluorinating agents such as HF, organic fluorinating agents such as hydrofluorocarbons (HFC) such as hexafluoropropylene, chlorofluorocarbons (CFC) such as chlorofluoromethane, and hydrochlorofluorocarbons (HCFC) can also be used.

[0070] As a method for fluorinating the activated carbon, for example, a method of flowing the above-mentioned fluorinating agent under atmospheric pressure under temperature conditions of room temperature (25 °C) to about 400 °C can be cited for fluorination.

[0071] As the Lewis acid catalyst, there is no particular limitation, and chromium oxide catalyst, alumina catalyst, silica-alumina catalyst, zeolite catalyst, etc. can be cited. These Lewis acid catalysts can be either unfluorinated Lewis acid catalysts or fluorinated Lewis acid catalysts.

[0072] Regarding the chromium oxide catalyst, there is no particular limitation. When chromium oxide is denoted as CrOm, it is preferably 1.5 < m < 3, more preferably 2 < m < 2.75, and even more preferably 2 < m < 2.3. In addition, when chromium oxide is denoted as CrO m ·nH2O, hydration can also be carried out in such a manner that the value of n is 3 or less, particularly 1 to 1.5.

[0073] The fluorinated chromium oxide catalyst can be prepared by fluorination of the above-mentioned chromium oxide catalyst. This fluorination can be carried out using, for example, HF, fluorohydrocarbons, etc. Such a fluorinated chromium oxide catalyst can be synthesized, for example, according to the method described in Japanese Patent Laid-Open No. 05-146680.

[0074] Hereinafter, an example of the synthesis method of the chromium oxide catalyst and the fluorinated chromium oxide catalyst will be illustrated.

[0075] First, a precipitate of chromium hydroxide is obtained by mixing an aqueous solution of a chromium salt (chromium nitrate, chromium chloride, chrome alum, chromium sulfate, etc.) with ammonia water. The physical properties of chromium hydroxide are controlled by the reaction rate of the precipitation reaction at this time. A fast reaction rate is preferred. The reaction rate is affected by the temperature of the reaction solution, the method of mixing ammonia water (mixing rate), the stirring state, etc.

[0076] After filtering and washing the precipitate, drying can be carried out. Drying can be carried out, for example, in air at 70 to 200 °C for 1 to 100 hours. Sometimes the catalyst at this stage is called the state of chromium hydroxide. Next, the catalyst can be crushed. From the viewpoints of the strength of the pellets and the activity of the catalyst, etc., it is preferred to adjust the precipitation reaction rate so that the powder density of the crushed powder (for example, the powder with a particle size of 1000 μm or less, especially the powder with a particle size of 46 to 1000 μm accounting for 95%) is 0.6 to 1.1 g / ml, preferably 0.6 to 1.0 g / ml. The specific surface area of the powder (the specific surface area measured by the BET method) is preferably 100 m 2 / g or more, more preferably 120 m 2 / g or more under the degassing conditions of 200 °C and 80 minutes. In addition, the upper limit of the specific surface area is, for example, about 220 m 2 / g.

[0077] The powder of chromium hydroxide is mixed with 3% by weight or less of graphite as needed and formed into pellets by a tablet press. The size and strength of the pellets can be appropriately adjusted.

[0078] The formed catalyst can be fired in an inert atmosphere gas, for example, in a nitrogen gas stream, to form amorphous chromium oxide. The firing temperature is preferably 360 °C or higher, and from the viewpoint of suppressing crystallization, it is preferably 380 to 460 °C. In addition, the firing time can be set to 1 to 5 hours, for example.

[0079] From the viewpoint of the activity of the catalyst, the specific surface area of the fired catalyst is preferably 170 m 2 / g or more, more preferably 180 m 2 / g or more, further preferably 200 m 2 / g or more. In addition, the upper limit of the specific surface area is usually preferably about 240 m 2 / g, more preferably about 220 m 2 / g.

[0080] Next, chromium fluoride is obtained by fluorinating chromium oxide. The fluorination temperature can be any temperature range as long as the generated water does not condense, and the upper limit is the temperature at which the catalyst does not crystallize due to the heat of reaction. The fluorination temperature can be set to 100 to 460 °C, for example. The pressure during fluorination is not limited, and it is preferably carried out at the pressure provided for the catalytic reaction.

[0081] As alumina catalysts, for example, α-alumina, activated alumina, etc. can be cited. As activated alumina, ρ-alumina, χ-alumina, κ-alumina, η-alumina, pseudo-γ-alumina, γ-alumina, σ-alumina, θ-alumina, etc. can be cited.

[0082] In addition, silica-alumina catalysts can also be used as composite oxides. Silica-alumina catalysts are composite oxide catalysts containing silica (SiO2) and alumina (Al2O3). When the total amount of silica and alumina is 100% by mass, for example, catalysts with a silica content of 20 to 90% by mass, particularly 50 to 80% by mass, can be used.

[0083] Alumina catalysts and silica-alumina catalysts exhibit stronger activity through fluorination. Therefore, the alumina catalyst can also be fluorinated in advance before use and used as a fluorinated alumina catalyst, and the silica-alumina catalyst can be fluorinated and used as a fluorinated silica-alumina catalyst.

[0084] As fluorinating agents for fluorinating alumina catalysts and silica-alumina catalysts, for example, inorganic fluorinating agents such as F2 and HF, fluorohydrocarbon-based organic fluorinating agents such as hexafluoropropene, etc. can be used.

[0085] As a method for fluorinating alumina catalysts and silica-alumina catalysts, for example, a method of flowing the above-mentioned fluorinating agent under atmospheric pressure under temperature conditions of room temperature (25°C) to about 400°C for fluorination can be cited.

[0086] As zeolite catalysts, publicly known types of zeolites can be widely used. For example, crystalline hydrated aluminosilicates of alkali metals or alkaline earth metals are preferred. The crystal form of the zeolite is not particularly limited, and A-type, X-type, LSX-type, etc. can be cited. The alkali metal or alkaline earth metal in the zeolite is not particularly limited, and potassium, sodium, calcium, lithium, etc. can be cited.

[0087] Zeolite catalysts exhibit stronger activity through fluorination. Therefore, the zeolite catalyst can be fluorinated in advance before use and used as a fluorinated zeolite catalyst.

[0088] As fluorinating agents for fluorinating zeolite catalysts, for example, inorganic fluorinating agents such as F2 and HF, fluorohydrocarbon-based organic fluorinating agents such as hexafluoropropene, etc. can be used.

[0089] As a method for fluorinating zeolite catalysts, for example, a method of flowing the above-mentioned fluorinating agent under atmospheric pressure under temperature conditions of room temperature (25°C) to about 400°C for fluorination can be cited.

[0090] The above catalysts can be used alone or in combination of two or more. Among these, from the viewpoints of conversion rate, selectivity and yield, fluorinated or non-fluorinated activated carbon catalysts, fluorinated or non-fluorinated chromium oxide catalysts, fluorinated or non-fluorinated alumina catalysts, etc. are preferred, and fluorinated or non-fluorinated activated carbon catalysts, fluorinated or non-fluorinated chromium oxide catalysts, etc. are more preferred.

[0091] In addition, when the above-mentioned fluorinated or non-fluorinated Lewis acid catalyst is used as a catalyst, it can also be supported on a carrier. Examples of such a carrier include carbon, alumina (Al2O3), zirconia (ZrO2), silica (SiO2), titanium oxide (TiO2), etc. As carbon, activated carbon, amorphous carbon, graphite, diamond, etc. can be used.

[0092] In the production method of the present invention, when a halogenated butyne compound is reacted with hydrogen halide in the presence of a catalyst, for example, it is preferred that the catalyst is brought into contact with the halogenated butyne compound in a solid state (solid phase). At this time, the shape of the catalyst can also be in powder form, but in the case of a gas-phase continuous flow reaction, granular form is preferred.

[0093] The specific surface area of the catalyst measured by the BET method (hereinafter, sometimes also referred to as "BET specific surface area") is usually preferably 10 - 3,000 m 2 / g, more preferably 10 - 2,500 m 2 / g, even more preferably 20 - 2,000 m 2 / g, and particularly preferably 30 - 1,500 m 2 / g. When the BET specific surface area of the catalyst is within this range, the density of the catalyst particles is not too small, so that the halogenated butene compound can be obtained with a higher selectivity. In addition, the conversion rate of the halogenated butyne compound can be further increased.

[0094] In the step of reacting the halogenated butyne compound with hydrogen halide in the present invention, from the viewpoints of more efficiently performing the addition reaction of hydrogen halide, further increasing the conversion rate, and obtaining the halogenated butene compound as the target compound with a higher selectivity, the lower limit value of the reaction temperature is usually preferably 180 °C or higher, more preferably 200 °C or higher. In addition, when a Lewis acid catalyst is used as the catalyst, for the same reason, the lower limit value of the reaction temperature is preferably 280 °C or higher, more preferably 320 °C or higher.

[0095] From the viewpoints of more efficiently performing the addition reaction of hydrogen halide, further increasing the conversion rate, and obtaining the butene halide compound as the target compound with a higher selectivity, and further suppressing the decrease in selectivity caused by the decomposition or polymerization of the reaction product, in the present invention, the upper limit value of the reaction temperature for reacting a butyne halide compound with hydrogen halide is generally preferably 500 °C or lower, more preferably 450 °C or lower, and still more preferably 400 °C or lower.

[0096] Regarding the reaction time for reacting a butyne halide compound with hydrogen halide in the present invention, from the viewpoint of obtaining a butene halide compound with a particularly high conversion rate, higher yield, and high selectivity of the reaction, for example, when using a gas-phase flow-through type, the contact time (W / F) of the raw material compound with respect to the catalyst (W: weight of the metal catalyst (g), F: flow rate of the raw material compound (cc / sec)) is preferably 1.5 to 30 g·sec. / cc, more preferably 1.8 to 20 g·sec. / cc, and still more preferably 2.0 to 10 g·sec. / cc. The above W / F is particularly determined according to the reaction time when using a gas-phase flow-through reaction. When using a batch reaction, the contact time can also be appropriately set. In addition, the above contact time refers to the time when the substrate and the catalyst are in contact.

[0097] From the aspect of more efficiently performing the addition reaction of hydrogen halide, in the present invention, the reaction pressure for reacting a butyne halide compound with hydrogen halide is preferably -0.05 MPa to 2 MPa, more preferably -0.01 MPa to 1 MPa, and still more preferably atmospheric pressure to 0.5 MPa. In addition, in the present invention, unless otherwise specified, the pressure is the gauge pressure.

[0098] In the reaction of a butyne halide compound with hydrogen halide in the present invention, as the reactor for charging the butyne halide compound and the catalyst to react, as long as it can withstand the above temperature and pressure, the shape and structure are not particularly limited. As the reactor, for example, a vertical reactor, a horizontal reactor, a multi-tubular reactor, etc. can be cited. As the material of the reactor, for example, glass, stainless steel, iron, nickel, iron-nickel alloy, etc. can be cited.

[0099] The reaction of a butyne halide compound with hydrogen halide (addition reaction of hydrogen halide) in the present invention can also be carried out by any of the flow-through type and batch type in which the substrate is continuously charged into the reactor and the target compound is continuously taken out from the reactor. Since the target compound remains in the reactor and further undergoes an elimination reaction, it is preferably carried out in a flow-through type. In the process of reacting a butyne halide compound with hydrogen halide in the present invention, it is preferably carried out in the gas phase, particularly in the gas-phase continuous flow-through type using a fixed-bed reactor. When carried out in the gas-phase continuous flow-through type, the device, operation, etc. can be simplified, which is economically advantageous.

[0100] Regarding the atmosphere gas during the reaction of the butynyl halide compound and hydrogen halide in the present invention, from the viewpoint of suppressing the deterioration of the catalyst, an inert gas atmosphere, a hydrogen fluoride gas atmosphere, etc. are preferred. Examples of such inert gases include nitrogen, helium, argon, etc. Among these inert gases, nitrogen is preferred from the viewpoint of cost suppression. The concentration of the inert gas is preferably set to 0 to 50 mol% of the gas components introduced into the reactor.

[0101] The target compound of the present invention obtained by such an operation is a butenyl halide compound represented by the general formula (1).

[0102] General formula (1):

[0103] CX 1 X 2 X 3 CX 4 =CHCX 7 X 8 X 9 (1)

[0104] [In the formula, X 1 , X 2 , X 3 , X 4 , X 7 , X 8 and X 9 are the same or different and represent halogen atoms.]

[0105] X 1 , X 2 , X 3 , X 7 , X 8 and X 9 in the general formula (1) correspond to X 1 , X 2 , X 3 , X 7 , X 8 and X 9 in the above general formula (2). In addition, in the general formula (1), examples of the halogen atom represented by X 4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Therefore, specific examples of the butenyl halide compound represented by the general formula (1) to be produced include CF3CF=CHCF3, CCl3CCl=CHCCl3, CBr3CBr=CHCBr3, etc.

[0106] After the reaction of the halogenated butyne compound with hydrogen halide (addition reaction of hydrogen halide) is completed, purification can be carried out according to a conventional method as needed to obtain the halogenated butene compound as the target compound. In addition, according to the production method of the present invention, as described above, the reaction of adding 2 moles of hydrogen halide per 1 mole of the halogenated butyne compound is suppressed, and the halogenated butene compound obtained by adding 1 mole of hydrogen halide per 1 mole of the halogenated butyne compound can be selectively obtained.

[0107] The halogenated butene compound obtained by such operation can be effectively used in various applications such as etching gases for forming the most advanced microstructures of semiconductors, liquid crystals, etc.

[0108] 2. Halogenated butene composition

[0109] By operating as described above, a halogenated butene compound can be obtained, and it can also be obtained in the form of a halogenated butene composition containing a halogenated butene compound obtained by adding 1 mole of hydrogen halide per 1 mole of the halogenated butyne compound and a halogenated butane compound obtained by adding 2 moles of hydrogen halide per 1 mole of the halogenated butyne compound.

[0110] In the halogenated butene composition of the present invention, the halogenated butene compound is the halogenated butene compound represented by the above general formula (1), and the halogenated butane compound is the halogenated butane compound represented by the above general formula (3).

[0111] In the general formulas (1) and (3), as X 1 、X 2 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 and X 9 The halogen atoms represented can include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

[0112] Taking the total amount of the halogenated butene composition of the present invention as 100 mol%, the content of the halogenated butene compound represented by the general formula (1) is preferably 91.00 to 99.99 mol%, more preferably 92.00 to 99.98 mol%. In addition, the content of the halogenated butane compound represented by the general formula (3) is preferably 0.01 to 9.00 mol%, more preferably 0.02 to 8.00 mol%.

[0113] In addition, when the butene halide composition is obtained by using the production method of the present invention, as described above, the conversion rate of the reaction can also be increased, and the butene halide compound represented by the general formula (1) can be obtained in a high yield and high selectivity. Therefore, the components other than the butene halide compound represented by the general formula (1) in the butene halide composition can be reduced, and thus the labor for purification for obtaining the butene halide compound represented by the general formula (1) can be reduced.

[0114] In addition to being used as an etching gas for forming the most advanced microstructures such as semiconductors and liquid crystals, the butene halide composition of the present invention can also be effectively used in various applications such as building blocks for organic synthesis. In addition, a building block for organic synthesis refers to a substance that can be a precursor of a compound having a highly reactive skeleton. For example, the butene halide composition of the present invention reacts with a fluorine-containing organosilicon compound such as CF3Si(CH3)3, and a fluoroalkyl group such as a CF3 group can be introduced to be converted into a substance that can be a cleaning agent or an intermediate for fluorine-containing pharmaceuticals.

[0115] As described above, the embodiments of the present invention have been described. Various changes can be made to the embodiments and details as long as they do not exceed the gist and scope of the claims.

[0116] Examples

[0117] Hereinafter, examples are illustrated to clarify the features of the present invention. The present invention is not limited to these examples.

[0118] In the production methods of the butene halide compounds of Examples 1 to 6 and Comparative Examples 1 to 2, the raw material compound is a butyne halide compound represented by the general formula (2), in which X 1 , X 2 , X 3 , X 7 , X 8 and X 9 are fluorine atoms, and the hydrogen halide is hydrogen fluoride. According to the following reaction formula, a butene halide compound is obtained through a hydrogen fluoride addition reaction:

[0119] CF3C≡CCF3 + HF → CF3CF=CHCF3

[0120] Examples 1 to 4: Hydrogen fluoride addition reaction using activated carbon catalyst

[0121] In a SUS pipe (outer diameter: 1 / 2 inch) used as a reaction tube, activated carbon catalyst (manufactured by Osaka Gas Chemical Co., Ltd.; specific surface area 1200 m 2 / g) 10 g. After drying at 200 °C for 2 hours under a nitrogen atmosphere, the pressure was set to atmospheric pressure, and CF3C≡CCF3 (substrate) and hydrogen fluoride gas were passed through the reaction tube in such a way that the contact time (W / F) of CF3C≡CCF3 (substrate) and hydrogen fluoride with the activated carbon catalyst was 2 g·sec / cc.

[0122] The reaction was carried out in a continuous gas-phase flow-through manner.

[0123] The reaction tube was heated to 200 °C, 250 °C, 300 °C, or 400 °C to initiate the hydrogen fluoride addition reaction.

[0124] The molar ratio of hydrogen fluoride gas in contact with CF3C≡CCF3 (substrate) (HF / CF3C≡CCF3 ratio) was set to 150, and the flow rates of the substrate and hydrogen fluoride gas were adjusted so that the contact time (W / F) was 2 g·sec / cc. The distillate passing through the decontamination tower was collected 1 hour after the start of the reaction.

[0125] Thereafter, mass spectrometry was performed using gas chromatography / mass spectrometry (GC / MS) with a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and structural analysis was performed using NMR spectra with an NMR (manufactured by JEOL Ltd., trade name "400YH").

[0126] Based on the results of mass spectrometry analysis and structural analysis, it was confirmed that CF3CF=CHCF3 was generated as the target compound. In Example 1, the conversion rate of CF3C≡CCF3 (substrate) was 99.75 mol%, the selectivity of CF3CF=CHCF3 (target compound) was 99.85 mol%, the selectivity of CF3CF2CH2CF3 was 0.11 mol%, and the selectivity of CF3CFHCFHCF3 was 0.01 mol%. In Example 2, the conversion rate of CF3C≡CCF3 (substrate) was 100.00 mol%, the selectivity of CF3CF=CHCF3 (target compound) was 99.36 mol%, the selectivity of CF3CF2CH2CF3 was 0.34 mol%, and the selectivity of CF3CFHCFHCF3 was 0.26 mol%. In Example 3, the conversion rate of CF3C≡CCF3 (substrate) was 100.00 mol%, the selectivity of CF3CF=CHCF3 (target compound) was 98.45 mol%, the selectivity of CF3CF2CH2CF3 was 0.98 mol%, and the selectivity of CF3CFHCFHCF3 was 0.10 mol%. In Example 4, the conversion rate of CF3C≡CCF3 (substrate) was 100.00 mol%, the selectivity of CF3CF=CHCF3 (target compound) was 99.15 mol%, the selectivity of CF3CF2CH2CF3 was 0.80 mol%, and the selectivity of CF3CFHCFHCF3 was 0.02 mol%.

[0127] Examples 5 to 6: Hydrogen fluoride addition reaction using chromium oxide catalyst

[0128] Using a chromium oxide catalyst (Cr2O3) as the catalyst, at a reaction temperature of 350 °C and a contact time (W / F) of 4 g·sec / cc or 5 g·sec / cc between CF3C≡CCF3 (substrate) and hydrogen fluoride gas with the chromium oxide catalyst, the total flow rate of CF3C≡CCF3 (substrate) and hydrogen fluoride gas was adjusted so that the molar ratio of hydrogen fluoride gas in contact with CF3C≡CCF3 (substrate) (HF / CF3C≡CCF3 ratio) was 50 or 200. Except for this, the reaction was carried out in the same manner as in Examples 1 to 4.

[0129] Based on the results of mass spectrometry analysis and structural analysis, it was confirmed that CF3CF=CHCF3 was generated as the target compound. In Example 5, the conversion rate of CF3C≡CCF3 (substrate) was 97.59 mol%, the selectivity of CF3CF=CHCF3 (target compound) was 99.98 mol%, the selectivity of CF3CF2CH2CF3 was 0.01 mol%, and the selectivity of CF3CFHCFHCF3 was 0.00 mol%. In Example 6, the conversion rate of CF3C≡CCF3 (substrate) was 80.90 mol%, the selectivity of CF3CF=CHCF3 (target compound) was 99.96 mol%, the selectivity of CF3CF2CH2CF3 was 0.03 mol%, and the selectivity of CF3CFHCFHCF3 was 0.00 mol%.

[0130] Comparative Examples 1 to 2: Hydrogen fluoride addition reaction without using catalyst

[0131] Without using a catalyst, the reaction temperature was 200 °C or 350 °C, the contact time (W / F) of CF3C≡CCF3 (substrate) and hydrogen fluoride gas with the catalyst was 20 g·sec / cc, and the molar ratio of CF3C≡CCF3 (substrate) to the hydrogen fluoride gas in contact therewith (HF / CF3C≡CCF3 ratio) was 200. Otherwise, the reaction was carried out in the same manner as in Examples 1 to 4. In Comparative Examples 1 to 2, setting W / F to 20 g·sec / cc means that CF3C≡CCF3 (substrate) was flowed at the same flow rate as when W / F was 20 g·sec / cc in Examples 1 to 6 using a catalyst.

[0132] Based on the results of mass spectrometry analysis and structural analysis, it was confirmed that CF3CF=CHCF3 was generated as the target compound. In Comparative Example 1, although the flow rate of CF3C≡CCF3 (substrate) was significantly greater than that in Examples 1 to 6, the conversion rate of CF3C≡CCF3 (substrate) was also 1.92 mol%, the selectivity of CF3CF=CHCF3 (target compound) was 90.83 mol%, the selectivity of CF3CF2CH2CF3 was 8.27 mol%, and the selectivity of CF3CFHCFHCF3 was 0.82 mol%. In Comparative Example 2, although the flow rate of CF3C≡CCF3 (substrate) was significantly greater than that in Examples 1 to 6, the conversion rate of CF3C≡CCF3 (substrate) was also 2.17 mol%, the selectivity of CF3CF=CHCF3 (target compound) was 85.52 mol%, the selectivity of CF3CF2CH2CF3 was 7.83 mol%, and the selectivity of CF3CFHCFHCF3 was 0.62 mol%. Therefore, the conversion rate of CF3C≡CCF3 (substrate) was significantly reduced, and CF3CF2CH2CF3 was generated as an impurity to a considerable extent, and the selectivity of CF3CF=CHCF3 as the target compound was also low.

[0133] The results are shown in Table 1.

[0134] [Table 1]

[0135]

Claims

1. A composition, characterized in that: it contains a halogenated butene compound represented by the general formula (1) and a halogenated butane compound represented by the general formula (3), assuming the total amount of the composition is 100 mol%, the content of the halogenated butene compound represented by the general formula (1) is 91.00 to 99.99 mol%, General formula (1): CX 1 X 2 X 3 CX 4 =CHCX 7 X 8 X 9 (1) In formula (1), X 1 , X 2 , X 3 , X 4 , X 7 , X 8 and X 9 are the same or different and represent a halogen atom, General formula (3): CX 1 X 2 X 3 CX 4 X 5 CHX 6 CX 7 X 8 X 9 (3) In formula (3), X 1 , X 2 , X 3 , X 4 , X 7 , X 8 , and X 9 are the same as above. One of X 5 and X 6 represents a hydrogen atom, and the other represents a halogen atom.

2. The composition according to claim 1, characterized in that: it is used as a cleaning gas, an etching gas or a building block for organic synthesis.

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