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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
  • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/06—Halogens; Compounds thereof
  • B01J27/08—Halides
  • B01J27/12—Fluorides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
  • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
  • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
  • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/06—Halogens; Compounds thereof
  • B01J27/08—Halides
  • B01J27/10—Chlorides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C19/00—Acyclic saturated compounds containing halogen atoms
  • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
  • C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine

Definitions

• the present invention relates to a novel method for producing 1,1,1,3,5,5,5-heptafluoro-2-pentene (hereinafter sometimes referred to as "HFO-1447”), and in particular, to a high purity 1,1 , 1,3,5,5,5-heptafluoro-2-pentene.
• HFO-1447 1,1,1,3,5,5,5-heptafluoro-2-pentene
• Fluoroolefins are used as solvents, detergents, blowing agents, and intermediates for functional materials, and various production methods have been proposed.
• HFC-458 1,1,1,3,3,5,5,5-octafluoropentane (hereinafter sometimes referred to as "HFC-458") HFO-1447 is produced by performing a dehydrofluorination reaction at a temperature of 330° C. using high-surface AlF 3 as a catalyst.
• Example 6 of Patent Document 1 describes that HFO-1447 was used in a blowing agent composition
• Example 7 describes that a mixed solvent containing HFO-1447 as a main component was used as a desiccant. has been done.
• bis(trifluoromethyl)arenes hereinafter simply referred to as "arene compounds”
• arene compounds bis(trifluoromethyl)arenes
• the purpose of the present invention is to provide a new method for producing 1,1,1,3,5,5,5-heptafluoro-2-pentene (hereinafter sometimes referred to as "HFO-1447"), In particular, it is an object of the present invention to provide a method for producing HFO-1447 with high purity (in particular, purity greater than 99%). It is also an object of the present invention to provide high purity HFO-1447 and its uses.
• HFO-1447 1,1,1,3,5,5,5-heptafluoro-2-pentene
• a method for producing 1,1,1,3,5,5,5-heptafluoro-2-pentene comprising: (a) 3-chloro-hexafluoro-2-pentene is reacted with hydrogen fluoride in the presence of a metal halide catalyst at a temperature above -10°C and below 20°C to produce 3-chloro-1,1,1 , 3,5,5,5-heptafluoropentane, and (b) the 3-chloro-1,1,1,3,5,5,5-heptafluoropentane obtained in (a) is heated on activated carbon.
• the method comprises carrying out a dehydrochlorination reaction in the presence of a catalyst to produce 1,1,1,3,5,5,5-heptafluoro-2-pentene.
• the metal halide catalyst is selected from an antimony halide catalyst, a tin halide catalyst, a titanium halide catalyst, a niobium halide catalyst, a tantalum halide catalyst, or a combination thereof.
• hydrogen fluoride is used in a molar equivalent ratio of 1 to 1.5 to 3-chloro-hexafluoro-2-pentene.
• step (a) The method according to [1], wherein the amount of the metal halide catalyst is 2 to 3 mol% based on 3-chloro-hexafluoro-2-pentene.
• step (a) The method according to [1], wherein the reaction in step (a) is carried out at a temperature of -5°C to 10°C.
• the metal halide catalyst is selected from antimony trichloride, antimony pentachloride, antimony trifluoride, antimony pentafluoride, tin tetrachloride, titanium tetrachloride, niobium pentafluoride, tantalum pentafluoride, or a combination thereof; -Hydrogen fluoride is used in a molar equivalent ratio of 1 to 1.5 with respect to chloro-hexafluoro-2-pentene, and the amount of metal halide catalyst is 2 to 1.5 with respect to 3-chloro-hexafluoro-2-pentene.
• step (a) High purity 1,1,1,3,5,5,5-heptafluoro-2-pentene obtained by the method described in any one of [1] to [7].
• step (9) High purity 1,1,1,3,5,5,5-heptafluoro-2-pentene according to claim 8, having a purity of more than 99%.
• the present inventors have discovered a method of efficiently obtaining high purity HFO-1447 by changing the manufacturing method. According to the present invention, there is no generation or contamination of arene compounds and HFC-458, and therefore HFO-1447 with high purity, particularly with a purity of over 99%, can be efficiently produced. HFO-1447 containing impurities produced by other manufacturing methods causes resin deterioration, but with the high purity HFO-1447 of the present invention, resin deterioration is suppressed and the range of applicable resins is expanded.
• FIG. 2 is a schematic diagram of a reaction apparatus used for the dehydrochlorination reaction in step (b).
• HFO-1447 1,1,1,3,5,5,5-heptafluoro-2-pentene
• Patent Document 1 HFO-1447 obtained by the method proposed in the prior art document (Patent Document 1) can be obtained from raw materials (HFC-458) and products that are difficult to separate from HFO-1447 through purification. (allene compound), making it impossible to efficiently obtain high-purity HFO-1447.
• the present inventors discovered (a) 3-chloro-1,1,1,5,5,5-hexafluoro-2-pentene (hereinafter referred to as "HCFO-1446”), which is easily available and easily separated from the product.
• HFO-1447 3-chloro-1,1,1,3,5, 3-chloro-1,1,1,3,5, 5,5-heptafluoropentane (hereinafter sometimes referred to as "HCFC-457"), and (b) the obtained 3-chloro-1,1,1,3,5,5,5-heptafluoro It has been found that by dehydrochlorinating pentane in the presence of an activated carbon catalyst to produce HFO-1447, HFO-1447 containing no arene compounds can be obtained. Since HFO-1447 obtained by the method of the present invention does not contain raw materials or products that are difficult to separate, it is possible to efficiently obtain HFO-1447 with a high purity that cannot be achieved using conventional techniques. Therefore, the high purity HFO-1447 of the present invention is itself a novel invention.
• step (a) 3-chloro-hexafluoro-2-pentene is reacted with hydrogen fluoride in the presence of a metal halide catalyst at a temperature above -10°C and below 20°C to produce 3-chloro-1, 1,1,3,5,5,5-heptafluoropentane is produced.
• Step (a) is characterized by employing specific raw materials and performing the fluorination reaction in the presence of a specific catalyst and within a specific temperature range.
• step (a) since only one molecule of hydrogen fluoride (HF) is added to the raw material, the target product can be selectively obtained with almost no by-products.
• HF hydrogen fluoride
• 3-chloro-hexafluoro-2-pentene which is a raw material for production, can be easily produced by a known method or easily obtained as a reagent.
• the metal halide catalyst examples include an antimony halide catalyst, a tin halide catalyst, a titanium halide catalyst, a niobium halide catalyst, a tantalum halide catalyst, and the like, which may be used alone or in combination of two or more. You can also use Examples of antimony halide catalysts include antimony trichloride, antimony pentachloride, antimony trifluoride, and antimony pentafluoride. Examples of tin halide catalysts include tin tetrachloride.
• titanium catalysts include titanium tetrachloride
• examples of niobium halide catalysts include niobium pentafluoride
• examples of tantalum halide catalysts include tantalum pentafluoride. , these can be used alone or in combination of two or more.
• Hydrogen fluoride to 3-chloro-hexafluoro-2-pentene is preferably used in a molar equivalent ratio of 0.5 to 10, more preferably 0.5 to 3, most preferably Preferably, they are used in a molar equivalent ratio of 1 to 1.5.
• the amount of the metal halide catalyst is preferably 0.1 to 10 mol%, more preferably 0.5 to 5 mol%. Most preferably, it is 2 to 3 mol%.
• the reaction temperature is above -10°C and below 20°C, more preferably between -10°C and 15°C, and most preferably between -5°C and 10°C.
• hydrogen fluoride can be liquefied and used as a solvent.
• the boiling point of hydrogen fluoride is approximately 20°C, so in the temperature range of step (a), it is a liquid phase reaction, so if the temperature is well controlled, the reaction can be carried out without using a pressure-resistant container such as an autoclave. be able to.
• step (b) the 3-chloro-1,1,1,3,5,5,5-heptafluoropentane obtained in step (a) is subjected to a dehydrochlorination reaction in the presence of an activated carbon catalyst to form HFO. -1447 is generated. In this dehydrochlorination reaction, only one molecule of hydrogen chloride is eliminated, so the product is only a mixture of E/Z isomers of HFO-1447.
• the activated carbon catalyst may be one commonly used for the dehydrochlorination reaction of halogenated alkanes, such as coconut shell charcoal for gas purification, catalysts and catalyst carriers (granular Shirasagi GX, SX, CX, XRC manufactured by Takeda Pharmaceutical Co., Ltd.). , PCB manufactured by Toyo Calgon, Yashicol, Kuraraycol GG, GC manufactured by Taihei Kagaku Sangyo Co., Ltd.), and these may be used alone or in combination of two or more. Since activated carbon is also used as a carrier, the activated carbon catalyst itself can be shaped into a desired shape without supporting the activated carbon on another carrier. Examples of the shape of the carrier include powder, granule, spherical, pellet, cylindrical, and honeycomb shapes.
• the contact time with the catalyst is usually 0.1 to 300 seconds, preferably 5 to 120 seconds, more preferably 10 to 60 seconds, but is not limited to this and may be changed as appropriate.
• the reaction temperature is preferably 150°C to 350°C, more preferably 200°C to 300°C, and most preferably 220°C to 250°C.
• a carrier gas is used for diluting raw material gas, drying a reactor, and the like.
• substances such as raw materials and reaction products can be moved within the reactor while adjusting their concentration by flowing a carrier gas.
• a carrier gas is selected that does not react with these substances. Examples include nitrogen, rare gases (helium, neon, argon, etc.).
• the carrier gas is usually 0 to 99%, more preferably 0 to 75%, most preferably 0 to 50% of the total flow rate of substances such as raw materials and reaction products. Mix and use in proportion.
• Examples of the material of the reaction device include corrosion-resistant metals such as stainless steel, Inconel, Monel, Hastelloy, and nickel. Among these, nickel is preferred from the viewpoint of corrosion resistance.
• catalysts of various shapes are filled in a cylindrical tube equipped with a heater for adjusting the reaction temperature, and the catalyst is directed from one end of the tube to the other.
• examples include those configured so that the raw material gas can flow through them. If the cylindrical tube loaded with the catalyst is extended vertically, the direction in which the raw material gas flows is to uniformly flow it little by little from top to bottom, which allows the raw material gas to flow little by little using gravity. Therefore, it is preferable.
• this apparatus is 3-chloro-1,1,1,3,5,5,5-heptachloro
• a raw material storage tank 1 that stores pentane
• a nitrogen cylinder 2 that supplies nitrogen gas to the evaporator 4
• a cylindrical catalyst tower 3 that is connected to the raw material storage tank by piping and installed vertically, and is installed just before the catalyst tower. It consists of an evaporator 4 and a collection tank 5 located downstream of the catalyst tower.
• 3-Chloro-1,1,1,3,5,5,5-heptachloropentane (boiling point 89°C) is heated as a liquid to a temperature above the boiling point using a syringe pump (not shown) in the evaporator 4. and is vaporized in the evaporator 4.
• the raw material gas is mixed with a carrier gas (nitrogen gas) in the evaporator 4, and while this mixed gas moves through the catalyst column from the top to the bottom, it comes into contact with the catalyst to promote the dehydrochlorination reaction.
• the reaction gas that has passed through the bottom of the catalyst tower passes through a collection tank filled with water, where the reaction products, unreacted raw materials, and hydrogen chloride are collected, and only the carrier gas is reacted. Expelled from the device.
• High purity HFO-1447 of the present invention can be obtained by distilling and purifying the reaction solution after performing step (b).
• High purity HFO-1447 obtained by the method of the present invention has two types of isomers, the (E)-isomer and the (Z)-isomer, each with a purity of over 99%, preferably 99.5%. % or more, more preferably 99.9% or more.
• "%" is a percentage by weight, with the total weight being 100%.
• the high-purity HFO-1447 of the present invention has low solubility in organic substances, particularly very low solubility in oil, but is compatible with organic solvents such as ethanol and 2-propanol. Utilizing this property, it is useful for the following applications.
• the high purity HFO-1447 of the present invention is suitable for use in ketones such as acetone and acetophenone, nitriles such as acetonitrile and propionitrile, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, and diglyme.
• ethers such as 1,4-dioxane, sulfoxides such as dimethyl sulfoxide and sulfolane, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, hydrocarbons such as hexane, heptane, cyclohexane, benzene and toluene, It can be mixed with organic solvents such as alcohols such as methanol, ethanol, and isopropanol in any proportion. Therefore, it can be used as a mixed solvent in a wide range of applications.
• the boiling points of the high purity HFO-1447 of the present invention are 52°C for the (E)-form and 78°C for the (Z)-form. Therefore, it can be easily volatilized and removed. Since the high-purity HFO-1447 of the present invention does not contain any arene compounds as impurities, the resin will not be cured during use, as verified in the Examples described later.
• More specific uses as a cleaning agent include the following three, for example.
• Particle cleaning A cleaning solution for removing fine particles from the surfaces of precision electronic devices, etc.
• Co-solvent cleaning This is a cleaning liquid for cleaning liquid crystal cells and liquid crystal panels, and for degreasing and drying processed parts.
• Cleaning for draining and drying This is a cleaning liquid for draining and drying lenses, sensor packages, semiconductor wafers, and other precision parts.
• the high purity HFO-1447 of the present invention has low surface tension (E form: 16.6 mN/m; Z form: 18.9 mN/m) and high specific gravity (E form: 1.41 g/cm 3 ; Z form: 1 .44g/cm 3 ), and is easy to dry. Therefore, it is suitable for particle cleaning. Furthermore, the high purity HFO-1447 of the present invention has low surface tension, low boiling point (E form: 52°C; Z form: 78°C), and nonflammability. Therefore, it is also suitable for co-solvent cleaning.
• the high purity HFO-1447 of the present invention has low latent heat of vaporization (anti-condensation), nonflammability, compatibility with existing cleaning agents (isopropanol), and high drying properties. Therefore, it is also suitable for draining and drying cleaning.
• thermosetting resins such as polyurethane
• thermoplastic resins such as polystyrene, polyethylene, and polypropylene
• Example 2 Example 3, Example 4, Example 5 (comparison), Example 6 (comparison)
• the reaction was carried out in the same manner as in Example 1, except that the reaction temperature, reaction time, and HF equivalent were changed as shown in Table 1. From the experimental results in Table 1, if a relatively low reaction temperature of 0 to 5°C, a relatively long reaction time of 24 to 48 hours, and an HF equivalent of 1 to 2 are used, the target HCFC It can be seen that -457 can be obtained with a yield of 70% or more.
• the selectivity for HCFC-457 is high even if the HF equivalent amount is greater than the theoretical amount for HCFO-1446, and at 5°C, the selectivity for HCFC-457 is high even if the HF equivalent amount is greater than the theoretical amount for HCFO-1446.
• -457 is further fluorinated to produce 1,1,1,3,3,5,5,5-octafluoropentane (HFC-458).
• HFC-458 1,1,1,3,3,5,5,5-octafluoropentane
• Example 7 1,1,1,3,5,5,5-heptafluoro-2 by de-HCl of 3-chloro-1,1,1,3,5,5,5-heptafluoropentane with activated carbon catalyst -Synthesis of pentene
• the apparatus shown in Figure 1 which uses a catalyst tower ( ⁇ 20.0 x 400 mm) filled with activated carbon pellets (Shirasagi C2X4/6-2) as a reactor, was heated with nitrogen at 250°C in the catalyst tower and 150°C in the evaporator.
• the total flow rate of the mixed gas of HCFC-457 and N2 was 125SCCM and the contact time was 60 seconds with activated carbon, and the product was collected in a collection tank containing 300 g of ice water cooled at -2 °C. . After supplying HCFC-457 for 47 minutes, the pump was stopped, and after white smoke was no longer observed in the collection tank, 23.22 g of the organic layer was collected from the collection tank.
• Example 9 (Comparative)] 1,1,1,3,5,5,5 - heptane by deHF reaction of 1,1,1,3,3,5,5,5-octafluoropentane with AlF3 catalyst Synthesis of fluoro-2-pentene
• HFC-458 3,5,5,5-octafluoropentane (HFC-458) was supplied at 35.8 ml/h (4.2 mmol/min, 94 SCCM), and the flow rate of the entire mixed gas of HFC-458 and N 2 was It was contacted with an AlF 3 catalyst at 125 SCCM and a contact time of 60 seconds, and the product was collected in a collection vessel containing 200 g of water cooled to -2°C. After supplying HFC-458 for 60 minutes, the pump was stopped, and after white smoke was no longer observed in the collection tank, 34.5 g of the organic phase was collected from the collection tank.
• Example 10 comparative
• Example 11 comparative
• the reaction was carried out in the same manner as in Example 9, except that the heating temperature of the catalyst tower was changed as shown in Table 2.
• the heating temperature of the catalyst tower was changed as shown in Table 2.
• the amount of allene compounds by-produced decreased, but the proportion of unreacted HFC-458 increased.
• Example 13 (comparative)] 1,1,1,3,5,5,5-heptafluoro by deHF reaction of 1,1,1,3,3,5,5,5-octafluoropentane using activated carbon catalyst -2-Synthesis of pentene
• the apparatus shown in Figure 1 which uses a catalyst tower ( ⁇ 20.0 x 400 mm) filled with activated carbon pellets (Shirasagi C2X4/6-2) as a reactor, was heated with nitrogen at 250°C in the catalyst tower and 150°C in the evaporator.
• 1,1,1,3,3,5,5,5-octafluoropentane (HFC-458) was supplied at 23.9 ml/h (2.8 mmol/min, 63 SCCM) while flowing at 63 SCCM.
• HFC-458 and N 2 were brought into contact with the activated carbon at a flow rate of 125 SCCM and a contact time of 60 seconds, and the product was collected in a collection tank containing 200 g of ice water cooled at -2°C. After supplying HFC-458 for 51 minutes, the pump was stopped, and after white smoke was no longer observed in the collection tank, 26.93 g of the organic phase was collected from the collection tank.
• the evaluation criteria are as follows. ⁇ : There was no corrosion/damage of the resin, no weight change, and no volume change. ⁇ : There was no corrosion or damage to the resin, but there were changes in weight and volume. ⁇ : There was corrosion and damage to the resin.
• Example 15 Resin material test for (E)-HFO-1447 containing 3% by weight of an arene compound was evaluated in the same manner as in [Example 14]. The results are shown in Table 3. The reason why the concentration of the allene compound was set to 3% by weight is that from the experimental results of Example 11 (comparison), (E)-HFO-1447 obtained by the production method of Patent Document 1 has the following properties: (E)-HFO-1447 This is because it is assumed that the arene compound is contained at a ratio of about 97% by weight:3% by weight.
• Example 17 Resin material test for (Z)-HFO-1447 containing 10% by weight of HFC-458 was evaluated in the same manner as in [Example 14] except that the heating temperature was 77°C. The results are shown in Table 4. The reason for setting the concentration of HFC-458 to 10% by weight is that from the experimental results of Example 11 (comparison), (Z)-HFO-1447 obtained by the manufacturing method of Patent Document 1 contains (Z)-HFO- This is because it was assumed that the ratio of 1447:HFC-458 was about 90% by weight: 10% by weight, and HFC-458 was included.
• Example 19 (Comparative) Elastomer material test for (E)-HFO-1447 containing 3% by weight of an allene compound was evaluated in the same manner as in [Example 14]. The results are shown in Table 5. The reason why the concentration of the allene compound was set to 3% by weight is that from the experimental results of Example 11 (comparison), (E)-HFO-1447 obtained by the production method of Patent Document 1 has the following properties: (E)-HFO-1447 This is because it is assumed that the arene compound is contained at a ratio of about 97% by weight:3% by weight.
• the production method of the present invention efficiently produces high purity (E)-HFO-1447 with no elastomer corrosion, weight change, and volume change, or with little weight change and volume change. I found out that it can be done.
• High purity (E)-HFO-1447 can be obtained by precision distillation using conventional production methods, but the yield is significantly reduced due to the removal of low-purity fractions.
• both (E) and (Z)-HFO-1447 produced by the method of the present invention are produced in a manner that does not contain by-products that are produced in the reaction system and are difficult to remove. It was discovered that by purifying the resin, deterioration of the resin can be suppressed and that it is suitable for use as a cleaning agent.

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