Process for producing halogenated butenyl compounds

Abstract

The present application provides a CX 1 X 2 X 3 CX 4 =CHCX 7 X 8 X 9 [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.] A method for producing a halogenated butene compound represented by the formula shown above, which includes reacting CX 1 X 2 X 3 C≡CCX 7 X 8 X 9 [In the formula, X 1 , X 2 , X 3 , X 7 , X 8 and X 9 are the same as described above.] A process for the reaction of a halogenated butyne compound represented by the formula shown above with hydrogen halide, which has a high conversion rate and is capable of obtaining a butene compound having 7 halogen atoms at a high selectivity.

Description

Technical Field

[0001] This invention relates to a method for manufacturing halobutene compounds. Background Technology

[0002] Butene compounds with seven halogen atoms, such as heptafluorobutene, are highly anticipated as dry etching gases for semiconductors, cleaning gases, and building blocks for organic synthesis.

[0003] As a method for producing the butene compound having 7 halogen atoms, for example, in Non-Patent Literature 1, after reacting CF3C≡CCF3 with AgF to obtain CF3CF=C(CF3)Ag, it is reacted with HCl in acetonitrile to obtain CF3CF=CHCF3.

[0004] Existing technical documents

[0005] Non-patent literature

[0006] Non-patent literature 1: Journal of the American Chemical Society, 91, 1969, pp. 6532-6534 Summary of the Invention

[0007] The technical problem that the invention aims to solve

[0008] The purpose of this invention is to provide a method for obtaining butene compounds with 7 halogen atoms with high conversion rate and high selectivity.

[0009] Technical solutions for solving technical problems

[0010] The present invention includes the following solutions.

[0011] Item 1. A method for producing a butene halide of formula (1), comprising the step of reacting a butyne halide of formula (2) with hydrogen halide in the presence of a catalyst.

[0012] General formula (1):

[0013] CX 1 X 2 X 3 CX 4 =CHCX 7 X 8 X 9 (1)

[0014] [In the formula, X] 1 X 2 X 3 X 4 X 7 X 8 and X9 The terms "same" or "different" indicate halogen atoms.

[0015] General formula (2):

[0016] CX 1 X 2 X 3 C≡CCX 7 X 8 X 9 (2)

[0017] [In the formula, X] 1 X 2 X 3 X 7 X 8 and X 9 Same as above.

[0018] Item 2. The manufacturing method as described in Item 1, wherein the halogenated butene compound represented by the above general formula (1) is CF3CF=CHCF3, and the halogenated butyne compound represented by the above general formula (2) is CF3C≡CCF3.

[0019] Item 3. The manufacturing method as described in Item 1 or 2, wherein the catalyst comprises at least one selected from fluorinated or non-fluorinated activated carbon catalysts and fluorinated or non-fluorinated Lewis acid catalysts.

[0020] Item 4. The manufacturing 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 selected from at least one of chromium oxide catalysts, alumina catalysts, silica-alumina catalysts and zeolite catalysts.

[0021] Item 5. The manufacturing method as described in any one of items 1 to 4, wherein 30 to 250 moles of hydrogen halide are reacted relative to 1 mole of the halobutyne compound represented by the above general formula (2).

[0022] Item 6. A composition comprising a butene halide of formula (1) and a butane halide of formula (3),

[0023] Assuming the total composition is 100 mol%, the content of the halogenated butene compound represented by the above general formula (1) is 91.00–99.99 mol%.

[0024] General formula (1):

[0025] CX 1 X 2 X 3 CX 4 =CHCX 7 X 8 X9 (1)

[0026] [In the formula, X] 1 X 2 X 3 X 4 X 7 X 8 and X 9 The terms "same" or "different" indicate halogen atoms.

[0027] General formula (3):

[0028] CX 1 X 2 X 3 CX 4 X 5 CHX 6 CX 7 X 8 X 9 (3)

[0029] [In the formula, X] 1 X 2 X 3 X 4 X 7 X 8 and X 9 Same as above. X 5 and X 6 One of them represents a hydrogen atom, and the other represents a halogen atom.

[0030] Item 7. The composition as described in Item 6, which is used as a cleaning gas, etching gas, or building block for organic synthesis.

[0031] The effects of the invention

[0032] According to the present invention, butene compounds having seven halogen atoms can be synthesized by a method that yields products with high conversion and high selectivity. Detailed Implementation

[0033] In this specification, "containing" includes any one of the following concepts: "comprise," "consistes essentially of," and "consist of." Furthermore, in this specification, when a numerical range is expressed as "A~B," it means above A and below B.

[0034] In this invention, "selectivity" 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 compounds other than the feedstock compound in the effluent gas.

[0035] In this invention, "conversion rate" refers to the ratio (mol%) of the total molar amount of compounds other than the feedstock compounds contained in the effluent gas from the reactor outlet to the molar amount of the feedstock compounds supplied to the reactor.

[0036] Currently, according to the method in Non-Patent Literature 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, this requires two steps and the total yield is only 57%.

[0037] Therefore, existing methods result in a yield of only 57% and involve numerous steps. The manufacturing method of this invention, compared to existing methods, enables the synthesis of butene compounds with seven halogen atoms through a process that yields the product with high conversion and high selectivity.

[0038] 1. Method for manufacturing halobutene compounds

[0039] The method for manufacturing the halobutene compound of the present invention is a method for manufacturing the halobutene compound represented by general formula (1), comprising a step of reacting the halobutyne compound of general formula (2) with hydrogen halide in the presence of a catalyst.

[0040] General formula (1):

[0041] CX 1 X 2 X 3 CX 4 =CHCX 7 X 8 X 9 (1)

[0042] [In the formula, X] 1 X 2 X 3 X 4 X 7 X 8 and X 9 The terms "same" or "different" indicate halogen atoms.

[0043] General formula (2):

[0044] CX 1 X 2 X 3 C≡CCX 7 X 8 X 9 (2)

[0045] [In the formula, X] 1 X 2 X 3 X7 X 8 and X 9 Same as above.

[0046] In the manufacturing method of the present invention, if the reaction of the halobutyne compound represented by general formula (2) with hydrogen halide is carried out without a catalyst, a halobutane compound represented by general formula (3) is generated as a byproduct to a considerable extent (e.g., more than 9.00 mol%) by adding 2 moles of hydrogen halide relative to 1 mole of the halobutyne compound represented by general formula (2).

[0047] General formula (3):

[0048] CX 1 X 2 X 3 CX 4 X 5 CHX 6 CX 7 X 8 X 9 (3)

[0049] [In the formula, X] 1 X 2 X 3 X 4 X 7 X 8 and X 9 Same as above. X 5 and X 6 One of them represents a hydrogen atom, and the other represents a halogen atom.

[0050] On the other hand, by reacting the halobutyne compound of general formula (2) with hydrogen halide in the presence of a catalyst, the addition of 2 moles of hydrogen halide to 1 mole of the halobutyne compound of general formula (2) can be suppressed, and the halobutene compound of general formula (1) can be selectively obtained, in which 1 mole of the halobutyne compound of general formula (2) has been added with 1 mole of hydrogen halide. This is because of the trihalomethyl (CX) 1 X 2 X 3 and CX 7 X 8 X 9 The trihalomethane trihalide possesses a strong electron-withdrawing effect. Due to this strong electron-withdrawing effect, the electron density of adjacent double and triple bonds decreases, thus making addition reactions to this unsaturated bond less likely. Halogenated butyne compounds, due to their triple bonds, are highly reactive and readily undergo addition reactions with hydrogen halides. However, halogenated butene compounds, due to the effect of the trihalomethane trihalide, do not react with hydrogen halides and do not form halogenated butane compounds, allowing for the selective formation of halogenated butene compounds.

[0051] The halogenated butyne compound that can be used as a substrate in the manufacturing method of the present invention, as described above, is a halogenated butyne compound represented by general formula (2).

[0052] General formula (2):

[0053] CX 1 X 2 X 3 C≡CCX 7 X 8 X 9 (2)

[0054] [In the formula, X] 1 X 2 X 3 X 7 X 8 and X 9 Same or different indicates halogen atoms.

[0055] In general formula (2), X is... 1 X 2 X 3 X 7 X 8 and X 9 The halogen atoms shown can be fluorine, chlorine, bromine, and iodine atoms.

[0056] As a substrate, halogenated butyne compounds, especially from the viewpoint of being able to produce halogenated butene compounds with high conversion, yield, and selectivity, are preferred. 1 X 2 X 3 X 7 X 8 and X 9 All are fluorine atoms.

[0057] The above X 1 X 2 X 3 X 7 X 8 and X 9 They can be the same or different.

[0058] Halogenated butyne compounds that satisfy the above conditions can specifically include CF3C≡CCF3, CCl3C≡CCCl3, CBr3C≡CCBr3, etc. These halogenated butyne compounds can be used alone or in combination of two or more. Such halogenated butyne compounds can be known or commercially available. Alternatively, they can be synthesized using conventional methods as described in Japanese Patent Application Publication No. 2012-001448, etc.

[0059] Examples of hydrogen halides that react with butyrynil compounds include hydrogen fluoride, hydrogen chloride, and hydrogen bromide. Furthermore, from the viewpoints of reaction conversion, yield, and selectivity, hydrogen fluoride is preferred. These hydrogen halides can be used alone or in combination of two or more.

[0060] Hydrogen halides are typically supplied to the reactor in a gaseous state along with the butyne halide compound (substrate). The amount of hydrogen halides supplied for reaction with the butyne halide compound (substrate) is preferably 30–250 moles, more preferably 35–240 moles, and even more preferably 40–230 moles, relative to 1 mole of the butyne halide compound (substrate). By setting this range, the addition reaction of hydrogen halides can proceed more effectively, and excessive addition of hydrogen halides can be further suppressed. This further reduces the formation of impurities, results in high selectivity for the butyne halide compound in the product, and allows for high-yield recovery.

[0061] In this invention, the step of reacting the halobutyne compound with hydrogen halide is an addition reaction of hydrogen halide, carried out in the presence of a catalyst. In the manufacturing method of this invention, the step of reacting the halobutyne compound with hydrogen halide (addition reaction) is preferably carried out in the gas phase, particularly in a continuous gas-phase flow-through manner using a fixed-bed reactor. Carrying it out in a continuous gas-phase flow-through manner simplifies the equipment and operation, and is economically advantageous.

[0062] In the step of reacting a halogenated butyne compound with hydrogen halide of the present invention, for example, as a substrate, the halogenated butyne compound represented by general formula (2) is more preferably X. 1 X 2 X 3 X 7 X 8 and X 9 It is a fluorine atom.

[0063] That is, preferably, the reaction is an addition reaction of hydrogen fluoride according to the following reaction formula.

[0064] CF3C≡CCF3+HF→CF3CF=CHCF3

[0065] The catalyst used in the manufacturing method of the present invention is preferably a fluorinated or non-fluorinated activated carbon catalyst, a fluorinated or non-fluorinated Lewis acid catalyst, etc.

[0066] As an activated carbon catalyst, there are no particular limitations; examples include crushed carbon, shaped carbon, granular carbon, and spherical carbon, among other powdered activated carbons. Powdered activated carbon with a particle size of 4 mesh (4.75 mm) to 100 mesh (0.150 mm) as shown in the JIS test (JIS Z8801) is preferred. These activated carbons can be well-known or commercially available products.

[0067] Activated carbon exhibits stronger activity through fluorination. Therefore, it is also possible to use fluorinated activated carbon obtained by previously fluorinating activated carbon before use in a reaction. That is, as an activated carbon catalyst, either non-fluorinated activated carbon or fluorinated activated carbon can be used.

[0068] As a fluorinating agent for fluorinating activated carbon, for example, in addition to inorganic fluorinating agents such as HF, organic fluorinating agents such as hydrofluorocarbons (HFCs) like hexafluoropropene, chlorofluorocarbons (CFCs) like chlorofluoromethane, and hydrochlorofluorocarbons (HCFCs) can also be used.

[0069] As a method for fluorinating activated carbon, for example, a method can be cited in which the above-mentioned fluorinating agent is passed under atmospheric pressure under temperature conditions of room temperature (25 °C) to about 400 °C for fluorination.

[0070] As a Lewis acid catalyst, there is no particular limitation, and examples include chromium oxide catalysts, alumina catalysts, silica-alumina catalysts, zeolite catalysts, etc. These Lewis acid catalysts can be either non-fluorinated Lewis acid catalysts or fluorinated Lewis acid catalysts.

[0071] 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. Additionally, when chromium oxide is denoted as CrO m ·nH2O, hydration can also be carried out such that the value of n is 3 or less, particularly 1 - 1.5.

[0072] 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.

[0073] Hereinafter, an example of a synthesis method for a chromium oxide catalyst and a fluorinated chromium oxide catalyst will be illustrated.

[0074] 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 reaction solution temperature, the method of mixing ammonia water (mixing rate), the stirring state, etc.

[0075] After filtering and washing the precipitate, it can be dried. Drying can be carried out in air at 70–200°C for 1–100 hours, for example. The catalyst at this stage is sometimes referred to as the chromium hydroxide state. Next, the catalyst can be broken down. From the viewpoint of particle strength and catalyst activity, it is preferable to adjust the precipitation reaction rate so that the density of the broken powder (e.g., 95% of which have a particle size of 1000 μm or less, particularly 46–1000 μm) is 0.6–1.1 g / ml, preferably 0.6–1.0 g / ml. The specific surface area of ​​the powder (measured by the BET method) is preferably 100 m² under degassing conditions at 200°C for 80 minutes. 2 / g or more, preferably 120m 2 / g or higher. Furthermore, the upper limit for specific surface area is, for example, 220m². 2 Approximately / g.

[0076] The chromium hydroxide powder is mixed with up to 3% by weight of graphite as needed, and then granulated using a tablet press. The size and strength of the granules can be adjusted appropriately.

[0077] The shaped catalyst can be calcined in an inert atmosphere, such as a nitrogen gas stream, to form amorphous chromium oxide. The calcination temperature is preferably 360°C or higher, and from the viewpoint of suppressing crystallization, 380–460°C is preferred. Furthermore, the calcination time can be set, for example, to 1–5 hours.

[0078] From the viewpoint of catalyst activity, the specific surface area of ​​the calcined catalyst is preferably, for example, 170 m². 2 / g or more, preferably 180m 2 / g or more, further preferably 200m 2 / g or more. Furthermore, the upper limit of the specific surface area is typically preferably 240 m². 2 Approximately 220 mg / g, more preferably 220 mg / g. 2 Approximately / g.

[0079] Next, fluorinated chromium oxide is obtained by fluorinating chromium oxide. The fluorination temperature can be any temperature range where the generated water does not condense, with the upper limit being the temperature at which the catalyst does not crystallize due to the heat of reaction. The fluorination temperature can be set, for example, from 100 to 460°C. There is no limitation on the pressure during fluorination, but it is preferable to use the pressure supplied for the catalytic reaction.

[0080] Examples of alumina catalysts include α-alumina and activated alumina. Examples of activated alumina include p-alumina, χ-alumina, κ-alumina, η-alumina, pseudo-γ-alumina, γ-alumina, σ-alumina, and θ-alumina.

[0081] 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 20-90% by mass, particularly 50-80% by mass, can be used.

[0082] Alumina catalysts and silica alumina catalysts exhibit enhanced activity through fluorination. Therefore, alumina catalysts can be fluorinated before use as fluorinated alumina catalysts, and silica alumina catalysts can be fluorinated as fluorinated silica alumina catalysts.

[0083] As a fluorinating agent for fluorinating alumina catalysts and silica alumina catalysts, for example, inorganic fluorinating agents such as F2 and HF, and fluorinated hydrocarbon-based organic fluorinating agents such as hexafluoropropylene can be used.

[0084] As a method for fluorinating alumina catalysts and silica alumina catalysts, for example, a method can be described in which the above-mentioned fluorinating agent is circulated under atmospheric pressure at a temperature of about room temperature (25°C) to about 400°C.

[0085] As zeolite catalysts, well-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 types such as A, X, and LSX can be listed. The alkali metal or alkaline earth metal in the zeolite is not particularly limited, and potassium, sodium, calcium, and lithium can be listed.

[0086] Zeolite catalysts exhibit enhanced activity through fluorination, thus allowing them to be pre-fluorinated and used as fluorinated zeolite catalysts before being used in reactions.

[0087] As fluorinating agents for fluorinating zeolite catalysts, inorganic fluorinating agents such as F2 and HF, and fluorinated hydrocarbon-based organic fluorinating agents such as hexafluoropropylene can be used.

[0088] As a method for fluorinating zeolite catalysts, for example, a method can be described in which the fluorinating agent is circulated under atmospheric pressure at a temperature of about room temperature (25°C) to 400°C.

[0089] The catalysts described above can be used alone or in combination of two or more. Among these, from the viewpoints of conversion, selectivity, and yield, fluorinated or non-fluorinated activated carbon catalysts, fluorinated or non-fluorinated chromium oxide catalysts, and fluorinated or non-fluorinated alumina catalysts are preferred, and fluorinated or non-fluorinated activated carbon catalysts and fluorinated or non-fluorinated chromium oxide catalysts are even more preferred.

[0090] Furthermore, when using the aforementioned fluorinated or non-fluorinated Lewis acid catalysts as catalysts, they can also be supported on a carrier. Examples of such carriers include carbon, alumina (Al₂O₃), zirconium oxide (ZrO₂), silicon dioxide (SiO₂), and titanium oxide (TiO₂). For carbon, activated carbon, amorphous carbon, graphite, and diamond can be used.

[0091] In the manufacturing method of the present invention, when the halobutyne compound reacts with hydrogen halide in the presence of a catalyst, it is preferable, for example, to contact the halobutyne compound in a solid state (solid phase). In this case, the catalyst can also be in powder form, but in a continuous gas-phase reaction, granular form is preferred.

[0092] The specific surface area of ​​the catalyst, as measured by the BET method (hereinafter sometimes referred to as "BET specific surface area"), is typically preferably 10 to 3,000 m². 2 / g, more preferably 10-2500m 2 / g, more preferably 20~2000m 2 / g, particularly preferably 30-1500m 2 / g. When the BET specific surface area of ​​the catalyst is within this range, the particle density of the catalyst will not be too low, thus enabling the production of butene halides with higher selectivity. Furthermore, the conversion rate of butyne halides can be further improved.

[0093] In the process of reacting a butyne halide compound with hydrogen halide in this invention, from the viewpoint of more efficiently carrying out the hydrogen halide addition reaction, further improving the conversion rate, and obtaining the butyne halide compound as the target compound with a higher selectivity, the lower limit of the reaction temperature is generally preferably 180°C or higher, more preferably 200°C or higher. Furthermore, when a Lewis acid catalyst is used as the catalyst, for the same reason, the lower limit of the reaction temperature is preferably 280°C or higher, more preferably 320°C or higher.

[0094] From the viewpoint of conducting the addition reaction of hydrogen halide more efficiently, further improving the conversion rate, obtaining the halobutene 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, the upper limit of the reaction temperature for reacting the halobutyne compound with hydrogen halide in this invention is generally preferably 500°C or less, more preferably 450°C or less, and even more preferably 400°C or less.

[0095] Regarding the reaction time for reacting the butyne halide compound with hydrogen halide in this invention, from the viewpoint of obtaining the butyne halide compound with particularly high conversion, higher yield, and high selectivity, for example, when using a gas-phase flow-through reaction, the contact time (W / F) [W: weight of metal catalyst (g), F: flow rate of the feed compound (cc / sec)] is preferably 1.5 to 30 g·sec. / cc, more preferably 1.8 to 20 g·sec. / cc, and even more preferably 2.0 to 10 g·sec. / cc. The above-mentioned W / F is determined specifically based on the reaction time when using a gas-phase flow-through reaction; the contact time can also be appropriately set when using a batch reaction. Furthermore, the above-mentioned contact time refers to the time of contact between the substrate and the catalyst.

[0096] From the perspective of more efficient addition reaction of hydrogen halide, the reaction pressure for reacting the butyryl halide compound with hydrogen halide in this invention is preferably -0.05 MPa to 2 MPa, more preferably -0.01 MPa to 1 MPa, and even more preferably atmospheric pressure to 0.5 MPa. Furthermore, in this invention, unless otherwise specified, the pressure is gauge pressure.

[0097] In the reaction of the halobutyne compound with hydrogen halide in this invention, the reactor used to carry the halobutyne compound and catalyst for the reaction can be any reactor capable of withstanding the aforementioned temperature and pressure; its shape and structure are not particularly limited. Examples of reactor types include vertical reactors, horizontal reactors, and multi-tube reactors. Examples of reactor materials include glass, stainless steel, iron, nickel, and iron-nickel alloys.

[0098] The reaction of the halobutyne compound with hydrogen halide (an addition reaction of hydrogen halide) in this invention can also be carried out in either a flow-through or batch manner by continuously feeding the substrate into the reactor and continuously removing the target compound from the reactor. The target compound remains in the reactor for further elimination reaction; therefore, a flow-through manner is preferred. In the process of reacting the halobutyne compound with hydrogen halide in this invention, it is preferably carried out in the gas phase, particularly in a continuous flow-through gas phase using a fixed-bed reactor. A continuous flow-through gas phase simplifies the apparatus and operation, and is economically advantageous.

[0099] Regarding the atmosphere used in the reaction of the halobutyne compound with hydrogen halide in this invention, from the viewpoint of suppressing catalyst degradation, an inert gas atmosphere, such as a hydrogen fluoride atmosphere, is preferred. Examples of inert gases include nitrogen, helium, and argon. Among these inert gases, nitrogen is preferred from the viewpoint of minimizing costs. The concentration of this inert gas is preferably set to 0-50 mol% of the gas composition introduced into the reactor.

[0100] The target compound of the present invention obtained by this operation is a butene halide compound represented by general formula (1).

[0101] General formula (1):

[0102] CX 1 X 2 X 3 CX 4 =CHCX 7 X 8 X 9 (1)

[0103] [In the formula, X] 1 X 2 X 3 X 4 X 7 X 8 and X 9 The terms "same" or "different" indicate halogen atoms.

[0104] X in general formula (1) 1 X 2 X 3 X 7 X 8 and X 9 X corresponds to the general formula (2) above. 1 X 2 X 3 X 7 X 8 and X 9 Additionally, in general formula (1), X is... 4 The halogen atoms shown can be fluorine, chlorine, bromine, and iodine. Therefore, the halogenated butene compounds of the general formula (1) to be manufactured can be specifically listed as CF3CF=CHCF3, CCl3CCl=CHCCl3, CBr3CBr=CHCBr3, etc.

[0105] After the reaction of the butyne halide compound with hydrogen halide (the addition reaction of hydrogen halide) is completed, the butene halide compound can be purified according to conventional methods as needed to obtain the desired compound. Furthermore, according to the manufacturing method of the present invention, as described above, the reaction of adding 2 moles of hydrogen halide to 1 mole of the butyne halide compound is suppressed, and a butene halide compound in which 1 mole of hydrogen halide has been added to 1 mole of the butyne halide compound can be selectively obtained.

[0106] The halogenated butene compounds obtained in this way can be effectively utilized in various applications, such as etching gases used to form the finest microstructures at the forefront of semiconductors, liquid crystals, etc.

[0107] 2. Halogenated butene composition

[0108] By operating as described above, a butene halide compound can be obtained, or it can be obtained as a butene halide compound containing 1 mole of hydrogen halide added to 1 mole of butyne halide compound and 2 moles of hydrogen halide added to 1 mole of butyne halide compound.

[0109] In the butene halide composition of the present invention, the butene halide compound is the butene halide compound represented by the above general formula (1), and the butane halide compound is the butane halide compound represented by the above general formula (3).

[0110] In general formulas (1) and (3), X is... 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 and X 9 The halogen atom shown can be fluorine, chlorine, bromine, or iodine, with fluorine being preferred.

[0111] The total amount of the halobutene composition of the present invention is set to 100 mol%, and the content of the halobutene compound shown in 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 halobutane compound shown in general formula (3) is preferably 0.01 to 9.00 mol%, more preferably 0.02 to 8.00 mol%.

[0112] Furthermore, when the manufacturing method of the present invention is used to obtain a halogenated butene composition, as described above, the conversion rate of the reaction can be improved, and the halogenated butene compound of general formula (1) can be obtained in high yield and with high selectivity. Therefore, it is possible to reduce the components other than the halogenated butene compound of general formula (1) in the halogenated butene composition, and thus, it is possible to reduce the labor required for purification to obtain the halogenated butene compound of general formula (1).

[0113] This halide butene composition of the present invention, in addition to being used as an etching gas for forming the fine structures at the forefront of semiconductors, liquid crystals, etc., can also be effectively utilized in various applications such as building blocks for organic synthesis. Furthermore, building blocks for organic synthesis refer to substances that can serve as precursors to compounds with highly reactive frameworks. For example, when the halide butene composition of the present invention reacts with fluorinated organosilicon compounds such as CF3Si(CH3)3, it can introduce fluorinated alkyl groups such as CF3 groups to transform into substances that can be used as cleaning agents and fluorinated pharmaceutical intermediates.

[0114] The embodiments of the present invention have been described above. Various changes can be made to the methods and details without departing from the spirit and scope of the claims.

[0115] Example

[0116] The following examples illustrate the features of the present invention. The present invention is not limited to these examples.

[0117] In the methods for producing halobutene compounds in Examples 1-6 and Comparative Examples 1-2, the raw material compound is a halobutyne compound represented by general formula (2), wherein X 1 X 2 X 3 X 7 X 8 and X 9 Compounds containing fluorine atoms and hydrogen fluoride as the hydrogen halide can be converted into butene halide compounds via hydrogen fluoride addition reactions according to the following reaction formula:

[0118] CF3C≡CCF3+HF→CF3CF=CHCF3

[0119] Examples 1-4: Hydrofluoric acid addition reaction using activated carbon catalyst

[0120] An activated carbon catalyst (manufactured by Osaka Gas Chemical Co., Ltd.; specific surface area 1200 m²) was added to the SUS piping (outer diameter: 1 / 2 inch) serving as the reaction tube. 2 10g. 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 were circulated in the reaction tube with a contact time (W / F) of 2 g·sec / cc with the activated carbon catalyst.

[0121] The reaction proceeds in a continuous gas-phase flow.

[0122] The reaction tube is heated to 200°C, 250°C, 300°C or 400°C to initiate the hydrogen fluoride addition reaction.

[0123] The molar ratio of hydrogen fluoride gas in contact with CF3C≡CCF3 (HF / CF3C≡CCF3 ratio) was set to 150. The flow rates of the substrate and hydrogen fluoride gas were adjusted with a contact time (W / F) of 2 g·sec / cc. The distillate that passed through the purging tower was collected 1 hour after the start of the reaction.

[0124] Subsequently, mass spectrometry analysis 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 spectroscopy with an NMR spectrometer (manufactured by JEOL Corporation, trade name "400YH").

[0125] Based on the results of mass spectrometry and structural analysis, CF3CF=CHCF3 was confirmed as the target compound. In Example 1, the conversion rate from 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 from 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 from CF3C≡CCF3 (substrate) was 100.00 mol%, the selectivity for CF3CF=CHCF3 (target compound) was 98.45 mol%, the selectivity for CF3CF2CH2CF3 was 0.98 mol%, and the selectivity for CF3CFHCFHCF3 was 0.10 mol%. In Example 4, the conversion rate from CF3C≡CCF3 (substrate) was 100.00 mol%, the selectivity for CF3CF=CHCF3 (target compound) was 99.15 mol%, the selectivity for CF3CF2CH2CF3 was 0.80 mol%, and the selectivity for CF3CFHCFHCF3 was 0.02 mol.

[0126] Examples 5-6: Hydrofluoric acid addition reaction using chromium oxide catalyst

[0127] A chromium oxide catalyst (Cr2O3) was used as the catalyst. The reaction temperature was 350°C, and the contact time (W / F) between CF3C≡CCF3 (substrate) and hydrogen fluoride gas with the chromium oxide catalyst was 4 g·sec / cc or 5 g·sec / cc. 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. Otherwise, the reaction was carried out in the same manner as in Examples 1 to 4.

[0128] The results of mass spectrometry and structural analysis confirmed that CF3CF=CHCF3 was generated as the target compound. In Example 5, the conversion rate from 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 from 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%.

[0129] Comparative Examples 1-2: Hydrofluoride Addition Reactions Without Catalysts

[0130] Without a catalyst, the reaction temperature was 200°C or 350°C, the contact time (w / f) between 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 contacting hydrogen fluoride gas (HF / CF3C≡CCF3 ratio) was 200. Otherwise, the reaction was carried out in the same manner as in Examples 1-4. Furthermore, in Comparative Examples 1-2, setting the w / f to 20 g·sec / cc means that the CF3C≡CCF3 (substrate) was flowed at the same flow rate as when the w / f was 20 g·sec / cc in Examples 1-6 using a catalyst.

[0131] The results of mass spectrometry and structural analysis confirmed that CF3CF=CHCF3 was generated as the target compound. In Comparative Example 1, although the flow rate of CF3C≡CCF3 (substrate) was significantly higher than that in Examples 1-6, the conversion rate from CF3C≡CCF3 (substrate) was 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 higher than that in Examples 1-6, the conversion rate from CF3C≡CCF3 (substrate) was 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 from CF3C≡CCF3 (substrate) was significantly reduced, and CF3CF2CH2CF3 was generated to a considerable extent as an impurity, while the selectivity of CF3CF=CHCF3 as the target compound was also low.

[0132] The results are shown in Table 1.

[0133] [Table 1]

[0134]

Claims

1. A method for manufacturing a butene halide compound represented by general formula (1), characterized in that: The method includes a step of reacting a halobutyne compound of general formula (2) with hydrogen fluoride at 180–500 °C in the presence of a catalyst, wherein the catalyst is at least one selected from fluorinated or non-fluorinated activated carbon catalysts and fluorinated or non-fluorinated chromium oxide catalysts. Relative to 1 mole of the halobutyne compound represented by general formula (2), react 30 to 250 moles of hydrogen fluoride. General formula (1): CX 1 X 2 X 3 CX 4 =CHCX 7 X 8 X 9 (1) In equation (1), X 1 X 2 X 3 X 4 X 7 X 8 and X 9 Represents a fluorine atom. General formula (2): CX 1 X 2 X 3 C≡CCX 7 X 8 X 9 (2) In equation (2), X 1 X 2 X 3 X 7 X 8 and X 9 Same as above.

2. The manufacturing method as described in claim 1, characterized in that: The catalyst is a fluorinated or non-fluorinated chromium oxide catalyst.

3. The manufacturing method as described in claim 1 or 2, characterized in that: The halogenated butene compound represented by general formula (1) is CF3CF=CHCF3, and the halogenated butyne compound represented by general formula (2) is CF3C≡CCF3.

Images