WO2019230456A1 - Procédé de production d'un propène contenant du fluor - Google Patents

Procédé de production d'un propène contenant du fluor Download PDF

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Publication number
WO2019230456A1
WO2019230456A1 PCT/JP2019/019762 JP2019019762W WO2019230456A1 WO 2019230456 A1 WO2019230456 A1 WO 2019230456A1 JP 2019019762 W JP2019019762 W JP 2019019762W WO 2019230456 A1 WO2019230456 A1 WO 2019230456A1
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fluorine
reaction
reducing agent
compound
production method
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PCT/JP2019/019762
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English (en)
Japanese (ja)
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敏史 仁平
慎哉 民辻
優 竹内
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Ａｇｃ株式会社
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Priority to JP2020522101A priority Critical patent/JP7287391B2/ja
Publication of WO2019230456A1 publication Critical patent/WO2019230456A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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

Definitions

  • the present invention relates to a method for efficiently producing a fluorine-containing propene.
  • HFCs hydrofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • fluorine-containing olefins such as hydrofluoroolefin (HFO) and hydrochlorofluoroolefin (HCFO) are attracting attention as compounds having a low global warming potential.
  • HFO and HCFO are known to have both low ozone depletion potential (ODP) and global warming potential (GWP). ing.
  • a C3 unsaturated compound (hereinafter also referred to as fluorine-containing propene) that is HFO or HCFO and has three carbons in its structure is preferable.
  • fluorine-containing propene a C3 unsaturated compound that is HFO or HCFO and has three carbons in its structure.
  • the fluorinated propene having a structure represented by —CF ⁇ in the molecule has low toxicity and is particularly suitable for refrigerants and solvents.
  • the fluorine-containing propene having a structure represented by —CF ⁇ CX 2 (in the molecule, two X's are each independently F, Cl or H, and both X are H) is Compared with fluorine-containing propene having a structure represented by —CF ⁇ CH 2 in the molecule, it has high nonflammability and excellent detergency, and is more suitable for refrigerants and solvents. Examples include 1-chloro-2,3,3,3-tetrafluoropropene (CF 3 —CF ⁇ CClH, HCFO-1224yd), 1-chloro-2,3,3 trifluoropropene (CF 2 H—CF ⁇ CClH) and the like.
  • a fluorinated propene having —CF ⁇ is produced, for example, by dechlorinating a fluorinated propane having —CFCl— as a precursor.
  • fluorinated propane having —CFCl— as a precursor is energetically unstable, it is difficult to obtain a fluorinated propene having —CF ⁇ in a high yield.
  • fluorine-containing propane starting from tetrafluoroethylene (TFE), which is a key raw material in the fluorine chemical industry, a compound having —CF 2 — is easily synthesized.
  • Patent Document 2 discloses a method of directly synthesizing a fluorinated propene having —CF ⁇ by using a fluorinated propane having —CF 2 — as a raw material and defluorinating and dechlorinating in an H 2 reducing atmosphere. It is being considered. However, in the method of Patent Document 2, the target fluorine-containing propene having —CF ⁇ is not obtained in high yield.
  • Non-Patent Document 1 a method of defluorinating and dechlorinating in the presence of metallic zinc has been attempted in the same manner as in Patent Document 2, but the same reaction system contains a substrate on which dechlorination proceeds, and the same. Since there are two defluorination and dechlorination routes in the substrate, the target fluorine-containing propene having —CF ⁇ cannot be obtained in high yield.
  • An object of the present invention is to provide a production method for efficiently obtaining a fluorine-containing propene having a —CF ⁇ structure in a high yield by using a fluorine-containing propane having a —CF 2 — structure as a raw material.
  • a fluorine-containing propene having a structure represented by —CF ⁇ CX 2 (X is independently F, Cl or H, except when both X are H) in the molecule It aims at providing the manufacturing method obtained efficiently and with a high yield.
  • a fluorine-containing chlorine-containing propane represented by the following formula (A) is defluorinated and dechlorinated in the presence of at least one reducing agent selected from alkaline earth metals and transition metals, and the following formula ( A method for producing a fluorinated propene, which obtains the fluorinated propene represented by B).
  • CY 3 -CF CX Formula 2 (B)
  • two Xs are each independently F, Cl or H
  • three Ys are each independently F or H. However, the case where both X are H is excluded.
  • X and Y in the formula (B) are the same as X and Y in the formula (A).
  • the fluorine-containing chlorine-containing propane is 3,3-dichloro-1,1,1,2,2-pentafluoropropane
  • the fluorine-containing propene is 1-chloro-2,3,3,3-tetra
  • the production method of [1] which is fluoropropene.
  • the production method of [1], wherein the fluorine-containing chlorine-containing propane is 1-chloro-1,1,2,2-tetrafluoropropane
  • the fluorine-containing propene is 1,1,2-trifluoropropene .
  • the fluorine-containing chlorine-containing propane is 1-chloro-1,1,2,2,3-pentafluoropropane
  • the fluorine-containing propene is 1,1,2,3-tetrafluoropropene
  • the manufacturing method of description [5] The method according to any one of [1] to [4], wherein the reducing agent includes at least one selected from the group consisting of zinc, magnesium, copper, and nickel.
  • the reducing agent contains zinc.
  • the reducing agent is a reducing agent activated with an activating agent.
  • the reducing agent has a particle size D 50 is a powder of 0.05 ⁇ 1000 .mu.m [1] one of the production method to [7]. [9] The production method of any one of [1] to [8], wherein the fluorine-containing chlorine-containing propane is defluorinated and dechlorinated in a liquid phase. [10] The method according to [9], wherein the liquid phase contains a solvent that dissolves the fluorine-containing chlorine-containing propane.
  • the solvent is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, N, N-dimethylformamide, acetonitrile, [10]
  • a process for producing [10] comprising at least one selected from the group consisting of acetone, methyl ethyl ketone, diethyl ketone, and tetrahydrofuran.
  • the production method according to any one of [1] to [11], wherein the reducing agent is used in a ratio of 0.6 to 3.0 mol with respect to 1.0 mol of the fluorine-containing chlorine-containing propane.
  • fluorine-containing propane having a —CF 2 — structure in the molecule is used as a raw material, —CF ⁇ structure, in particular, —CF ⁇ CX 2 (wherein X is independently F, Cl Or a fluorine-containing propene having a structure represented by the formula (except for the case where both X and H are both H), can be produced efficiently and in high yield under mild conditions.
  • Halogenated hydrocarbon is an abbreviation of the compound in parentheses after the compound name, and the abbreviation is used instead of the compound name as necessary.
  • the abbreviation only the number after the hyphen (-) and the lowercase alphabet part (for example, HCFO-1224yd may be represented by 1224yd.
  • (E) represents E form (trans form), and (Z) represents Z form (cis form) . If the E form or Z form is not specified in the name or abbreviation of the compound, the name or abbreviation is used. Means a generic name including E-form, Z-form, and a mixture of E-form and Z-form.
  • reaction formula (F) is referred to as reaction (F). Reactions represented by other formulas are also expressed accordingly.
  • the “compound represented by the formula (A)” is referred to as the compound (A). Compounds represented by other formulas are also represented accordingly.
  • “ ⁇ ” representing a numerical range includes the upper limit value and the lower limit value thereof. When the lower limit value and the upper limit value of the numerical range are the same unit, one of the descriptions may be omitted for the sake of brevity.
  • the particle size D 50 represents the particle size when the cumulative amount occupies 50% on the volume basis in the cumulative particle size curve of the particle size distribution measured using a laser diffraction / scattering type particle size distribution measuring apparatus.
  • the fluorine-containing chlorine-containing propane represented by the formula (A) is a reducing agent composed of at least one selected from alkaline earth metals and transition metals (hereinafter also referred to as a reducing agent (M)).
  • a reducing agent (M) a reducing agent
  • F reaction The defluorination dechlorination reaction (hereinafter also referred to as deClF reaction) according to the present invention is represented by the following reaction formula (F).
  • two Xs in the compound (A) are each independently F, Cl or H, and three Ys are each independently F or H.
  • the compound (A) does not include the case where both X are H.
  • X and Y in the compound (B) are the same as X and Y in the compound (A).
  • the present inventors obtain a fluorine-containing propene having a —CF ⁇ structure in the molecule in the presence of a reducing agent from a fluorine-containing chlorine-containing propane having a —CF 2 — structure in the molecule. It was found that the compound (B) as a product can be obtained in high yield by limiting the raw material to the compound (A) and combining the reducing agent with the reducing agent (M).
  • the de-ClF reaction has hitherto been recognized as being a simple method with a small number of reaction steps, but is not suitable as a method for producing a fluorinated propene with a very low yield.
  • compound (A) is subjected to deClF reaction using hydrogen as a reducing agent to obtain compound (B), but the yield is less than 50%.
  • Non-Patent Document 1 for example, CClF 2 —CF 2 —CCl 2 H having a structure different from that of the compound (A) is used as a raw material, and the compound (B) is subjected to a deClF reaction using a reducing agent (M). Although several types are obtained, the yield of the compound (B) is several percent or less in total. Thus, it has been said that the compound (B) cannot be obtained in a high yield by the deClF reaction proposed so far.
  • the present inventors first focused on the raw material of the deClF reaction using a reducing agent, and limited the structure of the raw material to the structure of the compound (A), that is, in CY 3 —CF 2 —CClX 2 , It was thought that by using a raw material limited to F, Cl or H and Y limited to F or H, side reactions were suppressed as follows.
  • F is extracted from —CF 2 — by the reducing agent, and at the same time, out of carbon atoms at both ends. Cl bonded to one of the carbon atoms is extracted.
  • the raw material compound (A) has a configuration in which Cl is bonded to only one of the terminal carbon atoms so that unnecessary side reactions do not occur.
  • the compound (B) in the deClF reaction (F) according to the production method of the present invention, can be produced in a high yield of 60% or more. Furthermore, in the deClF reaction (F) according to the production method of the present invention, the compound (B) can be obtained in a higher yield under milder conditions such as lowering the reaction temperature.
  • reaction to which the production method of the present invention can be applied Specific examples of the reaction to which the present invention is applied include deClF reactions represented by the following formulas (1) to (20).
  • the present invention is suitable.
  • it is particularly suitable for deClF reactions (8), (17) and (18).
  • the deClF reaction (8) is performed from 3,3-dichloro-1,1,1,2,2-pentafluoropropane (CF 3 —CF 2 —CCl 2 H, HCFC-225ca; hereinafter also referred to as 225ca). , 1-chloro-2,3,3,3-tetrafluoropropene (CF 3 —CF ⁇ CClH, HCFO-1224yd; hereinafter also referred to as 1224yd).
  • 1224yd is a compound that is expected to be used particularly for refrigerants and solvents.
  • Patent Document 1 also proposes a production route from 225ca.
  • dehydrofluorination, H 2 reduction, chlorination and dehydrochlorination are necessary, and there are problems that the number of steps is large and the production cost is high.
  • M 225ca reducing agent
  • the deClF reaction (17) is carried out from 1-chloro-1,1,2,2-tetrafluoropropane (CH 3 —CF 2 —CCIF 2 , HCFC-244cc, hereinafter also referred to as 244 cc) to 1,1,1,
  • This is a reaction for obtaining 2-trifluoropropene (CH 3 —CF ⁇ CF 2 , HFO-1243yc, hereinafter also referred to as 1243yc).
  • 1243yc is a compound that has not been described in the literature regarding production so far, but according to the production method of the present invention, it is possible to carry out in one step by deClF reaction using 244 cc of reducing agent (M), which is an easily available raw material. In addition, it can be produced in a high yield. 1243yc is useful for applications such as refrigerants, foaming agents, aerosol propellants, resin raw materials for car air conditioners and vending machines, for example.
  • the deClF reaction (18) is carried out from 1-chloro-1,1,2,2,3-pentafluoropropane (CH 2 F—CF 2 —CClF 2 , HCFC-235 cc, hereinafter also referred to as 235 cc) to 1 , 1,2,3-tetrafluoropropene (CH 2 F—CF ⁇ CF 2 , HFO-1234yc, hereinafter also referred to as 1234yc).
  • 1234yc is a compound that has not been described in the literature with respect to production so far, but according to the production method of the present invention, it can be obtained in one step by deClF reaction using 235 cc of a reducing agent (M), which is an easily available raw material. In addition, it can be produced in a high yield. 1234yc is useful, for example, for applications such as refrigerants, foaming agents, aerosol propellants, resin raw materials for car air conditioners and vending machines.
  • M reducing agent
  • the deClF reaction for obtaining the compound (B) from the compound (A) represented by the deClF reaction formulas (1) to (20) is performed at least selected from alkaline earth metals and transition metals. It is characterized in that it is carried out in the presence of one reducing agent (M).
  • 225ca is, for example, a reaction between tetrafluoroethylene (TFE) and dichlorofluoromethane (CCl 2 FH) in the presence of a Lewis acid catalyst such as aluminum chloride. Can be manufactured.
  • 225ca is 1,3-dichloro-1,1,2,2,3-pentafluoropropane (CClF 2 -CF 2 -CClFH, HCFC-225cb), 2,2-dichloro-1,1,3 , 3,3-pentafluoropropane (CHF 2 —CCl 2 —CF 3 , HCFC-225aa), 2,3-dichloro-1,1,2,3,3-pentafluoropropane (CHF 2 —CClF—CClF 2) , HCFC-225bb) and the like in a dichloropentafluoropropane (HCFC-225) isomer mixture. Therefore, 225ca is separated from the HCFC-225 isomer mixture by a known method such as distillation and used as the compound (A).
  • 225ca is distilled from a commercially available HCFC-225 isomer mixture containing 225ca, such as Asahiklin AK225 (AGC brand name, a mixture of 48 mol% of 225ca and 52 mol% of HCFC-225cb), etc.
  • the compound (A) may be used after being separated by the above method.
  • 244 cc in the reaction of the formula (17) to which the present invention is preferably applied can be produced, for example, by the following method (A) or method (B).
  • 244 cc is obtained as a reaction product containing unreacted raw materials, by-products and the like together with 244 cc. Therefore, 244 cc is separated and used as the compound (A) by a known purification process such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-layer separation, and adsorption.
  • 235 cc in the reaction of the formula (18) to which the present invention is preferably applied can be produced by, for example, the method described in US Pat. No. 5,756,869. That is, it can be produced by hydrogenating 225cb by reacting with hydrogen in the presence of a bismuth-palladium catalyst supported on activated carbon.
  • the reaction product contains an isomer such as 225ca and HCFC in which the isomer is hydrogenated
  • 235 cc is separated and used as the compound (A) by a known purification step such as distillation.
  • compound (A) may be used for deClF reaction (F) in the form of a mixture containing compound (A) and impurities.
  • the amount of impurities in the mixture is preferably set so as not to affect the effect of the production method of the present invention.
  • the compound (A) may be used together with by-products and unreacted raw materials that are by-produced during the production of the compound (A).
  • the composition containing the compound (A) having a purity of 85% by mass or more, preferably 90% by mass or more, and particularly preferably 95% by mass or more can be used in the present invention.
  • the reducing agent (M) used in the present invention is at least one selected from alkaline earth metals and transition metals.
  • the alkaline earth metal is beryllium, magnesium, calcium, strontium, barium, or radium.
  • the transition metal is a Group 3 element to a Group 12 element.
  • the reducing agent (M) is preferably zinc, magnesium, copper, or nickel from the viewpoint of reactivity, more preferably zinc or magnesium, and particularly preferably zinc from the viewpoint of handling properties.
  • a reducing agent (M) may consist of 1 type of the said metal, and may consist of 2 or more types. In the case of 2 or more types, it may be a mixture or an alloy.
  • the form of a reducing agent (M) is not specifically limited, From a viewpoint of contact efficiency with a compound (A), it is preferable that it is a powder form, and the more nearly spherical powder form is preferable.
  • the particle size is selected from the contact efficiency with the compound (A) and the ease of handling.
  • the particle size D 50 is preferably 0.05 to 1000 ⁇ m. The smaller the particle size, the better the contact efficiency between the compound (A) and the reducing agent (M), and the reaction proceeds, preferably 500 ⁇ m or less, more preferably 200 ⁇ m or less.
  • the handling at the time of manufacture becomes easy so that a particle size is large, 0.1 micrometer or more is more preferable, and 0.5 micrometer or more is further more preferable.
  • the surface of the metal constituting the reducing agent (M) is easily oxidized by exposure to oxygen in the air. Therefore, the reducing agent (M) usually has a constituent metal oxide film on its surface. When it has an oxide film, the reducing ability of a reducing agent (M) may fall and reaction rate may fall. Therefore, the reducing agent (M) is preferably subjected to a pretreatment for removing the oxide film before being used in the present invention.
  • an activator In order to remove the oxide film from the reducing agent (M), an activator is usually used.
  • an activator As the activator, an activator generally used for removing the oxide film on the metal surface can be used without particular limitation, and zinc chloride is suitable industrially. This is because, for example, when the deClF reaction according to the present invention is carried out in the liquid phase, the solubility of zinc chloride in a polar solvent is high, and particularly when zinc is used as the reducing agent (M), Since zinc chloride is produced as a by-product, there is no need to newly add an activator.
  • zinc chloride functions as an activator is that hydrogen chloride generated due to moisture contained in a trace amount in the reaction system removes the oxide film on the metal surface.
  • dibromoethane can also be used as an activator.
  • the amount of the activator is preferably 1 to 100 mol%, more preferably 10 to 50 mol%, and further preferably 20 to 50 mol% from the viewpoints of economy and reactivity with respect to the reducing agent (M). preferable.
  • the reducing agent (M) decreases during the reaction.
  • the amount is preferably from 1 to 100 mol%, more preferably from 10 to 50 mol% from the viewpoint of economy and reactivity, with respect to the maximum molar amount of the reducing agent (M) during the reaction.
  • the amount of the reducing agent (M) used in the present invention is preferably 0.6 to 3.0 mol with respect to 1.0 mol of the compound (A).
  • a compound (B) can be manufactured with a sufficiently high yield.
  • the amount used is more preferably 0.6 to 1.5 mol, particularly preferably 0.8 to 1.2 mol, and 1.0 to 1.2 mol, relative to 1.0 mol of compound (A). Is most preferred.
  • the reaction rate of the deClF reaction is low, and the production efficiency of the compound (B) may be low.
  • the reaction rate can be increased by increasing the reaction temperature, but the reaction rate can be increased by using a catalyst to improve the production efficiency of the compound (B).
  • the reaction rate is lower than the deClF reaction using 225ca according to the above formula (8). High temperature is required. Therefore, by using a catalyst, deClF reaction proceeds under milder conditions, and it is possible to obtain 1243yc as compound (B).
  • copper halide is preferred.
  • copper (I) chloride, copper (I) bromide, or copper (I) iodide is preferable, and copper bromide (I) is more preferable.
  • a catalyst obtained by complexing copper halide, particularly copper (I) bromide, with triphenylphosphine or the like is more preferable. By using the catalyst thus complexed, it becomes possible to obtain the compound (B) which is a deClF form with higher yield.
  • the amount used is preferably 1 mol% to 50 mol%, more preferably 5 mol% to 20 mol%, relative to compound (A).
  • the deClF reaction in the present invention may be performed in the liquid phase or in the gas phase.
  • the deClF reaction (F) is preferably carried out in a liquid phase from the viewpoint that it is easy to remove the halide of the reducing agent (M) by-produced in the deClF reaction represented by the above reaction formula (F).
  • the reaction formula (F) is shown as follows.
  • Y and X are the same as in reaction formula (F).
  • CY 3 —CF 2 —CClX 2 + Zn ⁇ CY 3 -CF CX 2 + 0.5ZnF 2 + 0.5ZnCl 2 Zinc, which is the reducing agent (M) in the above reaction formula, reacts with F and Cl generated by the deClF reaction of the compound (A), respectively, to generate zinc fluoride and zinc chloride. Therefore, the product after the reaction is compound (B), zinc fluoride and zinc chloride.
  • the liquid phase preferably contains a solvent.
  • the solvent is preferably a solvent that is non-reactive with the compound (A) and the resulting compound (B) and that dissolves the compound (A).
  • dissolves a compound (A) means that when a solvent and a compound (A) are mixed in arbitrary mixing ratios at 25 degreeC, it will melt
  • the solvent further dissolves the chloride and fluoride of the reducing agent (M) by-produced in the deClF reaction (F).
  • the solvent used for the deClF reaction (F) is preferably a polar solvent.
  • the polar solvent is preferably at least one selected from the group consisting of alcohols, ethers, ketones, amide compounds, and nitrile compounds.
  • Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol and the like.
  • Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone.
  • ether examples include chain ethers such as tetraethylene glycol dimethyl ether, dimethyl ether, ethyl methyl ether, diethyl ether, and ethylene oxide, and cyclic ethers such as tetrahydrofuran, furan, and crown ethers.
  • chain ethers such as tetraethylene glycol dimethyl ether, dimethyl ether, ethyl methyl ether, diethyl ether, and ethylene oxide
  • cyclic ethers such as tetrahydrofuran, furan, and crown ethers.
  • amide compound examples include N, N-dimethylformamide
  • nitrile compound examples include acetonitrile.
  • methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, N, N-dimethylformamide, acetonitrile, Acetone, methyl ethyl ketone, diethyl ketone, or tetrahydrofuran is preferred.
  • methanol, ethanol, tetrahydrofuran, acetone, N, N-dimethylformamide, or acetonitrile is used from the viewpoint of promoting the deClF reaction (F), availability, and ease of separation from the compound (B) after the deClF reaction.
  • an appropriate solvent can be selected from these in consideration of the reaction temperature and the degree of progress of side reactions.
  • These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the solvent used is preferably 10 to 2000 parts by mass, more preferably 20 to 1500 parts by mass with respect to 100 parts by mass of the compound (A), and 50 More preferred is ⁇ 500 parts by mass.
  • the reaction temperature of the deClF reaction (F) in the present invention depends on the type of the compound (A), but it is 0 to 250 ° C. from the viewpoint of increasing the reaction rate and the yield of the compound (B) regardless of the liquid phase or the gas phase. Is preferred. If the reaction temperature is too low, the reaction rate decreases and productivity decreases. Moreover, since decomposition
  • the reaction temperature is preferably 20 to 150 ° C, more preferably 50 to 100 ° C.
  • the reaction pressure is the pressure in the reactor for carrying out the reaction, and the gauge pressure is preferably 0 to 1 MPa, more preferably 0 to 0.5 MPa.
  • the reaction temperature is preferably 50 to 250 ° C., more preferably 100 to 200 ° C.
  • the reaction pressure is the pressure in the reactor for carrying out the reaction, and the gauge pressure is preferably 0 to 1 MPa, more preferably 0 to 0.5 MPa.
  • the reaction temperature is preferably 50 to 250 ° C, more preferably 100 to 200 ° C.
  • the reaction pressure is the pressure in the reactor for carrying out the reaction, and the gauge pressure is preferably 0 to 1 MPa, more preferably 0 to 0.5 MPa.
  • the reaction time for the deClF reaction (F) in the present invention is selected from the viewpoint of the yield of the compound (B) and the reaction rate, and the time with the highest productivity is selected. 10 hours is more preferable, and 2 to 5 hours is particularly preferable.
  • the production method of the present invention may be carried out by any of batch, semi-continuous or continuous methods.
  • the semi-continuous type can be exemplified by a fixed bed flow reactor type in which the compound (A) is continuously passed through the reactor filled with the reducing agent (M).
  • a de-ClF reaction (F) is carried out by installing a stirring blade in a batch, semi-continuous or continuous reactor and stirring it. It is preferable.
  • the reactor is not particularly limited as long as it can withstand the temperature and pressure in the reactor described above. For example, a flask, an autoclave, or a cylindrical vertical reactor can be used.
  • stirring blade examples include a 2-paddle blade, a 4-paddle blade, an anchor blade, a gate blade, a 3-propeller, a ribbon blade, and a 6-turbine blade.
  • the reactor may be provided with an electric heater for heating the inside of the reactor.
  • the production method of the present invention is carried out in the liquid phase, it is usually carried out by introducing a predetermined amount of the compound (A), the solvent, the reducing agent (M) and, if necessary, the activator and catalyst into the reactor.
  • the material of the reactor is a material that is inert to the reaction liquid component containing the compound (A), the solvent, the reducing agent (M), the catalyst, the compound (B), and the halide of the reducing agent (M), and is corrosion resistant. If it is, it will not be restrict
  • glass or an alloy such as stainless steel mainly containing iron, nickel, iron, or the like can be given.
  • the reaction product obtained by performing the deClF reaction (F) in the reactor includes, in addition to the target product compound (B), unreacted compound (A), by-product, solvent, reduction Agent (M), activator, catalyst may be included.
  • a separation and purification method such as filtration or distillation.
  • a reactive distillation format in which distillation is performed simultaneously with the deClF reaction can also be employed.
  • 1224yd obtained by deClF reaction from 225ca is obtained as a mixture of 1224yd (E) and 1224yd (Z). If necessary, 1224yd (E) and 1224yd (Z) may be separated and used by a general method such as distillation.
  • Example 1 Production of 1224yd by DeClF Reaction of 225ca [Production of 225ca]
  • TFE tetrafluoroethylene
  • CCl 2 FH dichlorofluoromethane
  • AlCl 3 Lewis acid aluminum chloride
  • a / C was installed in the water bath, and it heated up to 75 degreeC which is reaction temperature.
  • the temperature was raised in less than 1 hour, and the stirring blade was rotated at 300 rpm during the temperature rise and during the reaction.
  • the stirring blades used were two paddle blades.
  • the temperature was controlled at ⁇ 1 ° C., and the mixture was stirred for 4 hours.
  • the deClF form is a low-boiling compound (boiling point of about 15 ° C.), so the reaction pressure gradually increases, but the reaction was carried out in a sealed state without purging.
  • Example 2 Production of 1243yc by 244cc deClF [production of 244cc] Tetrafluoroethylene (TFE) and chloroform (CHCl 3 ) are reacted in the presence of a Lewis acid, and 1,1,3-trichloro-2,2,3,3-tetrafluoropropane ( HCFC-224ca (hereinafter also referred to as 224ca) was produced, and 244 cc was produced from the obtained 224ca by the second step.
  • TFE Tetrafluoroethylene
  • CHCl 3 chloroform
  • 224ca was produced by the following procedure.
  • CHCl 3 + TFE ⁇ 224ca anhydrous aluminum chloride (25 g, 0.19 mol), CHCl 3 (500 g, 4.19 mol) and 224ca (100 g, 0.45 mol) were put into 500 mL stainless steel A / C and degassed under reduced pressure while stirring.
  • TFE was supplied until the inside of A / C reached 0.05 MPa, and the inside of A / C was heated to 80 ° C. Thereafter, TFE was further supplied while maintaining the pressure in A / C at 0.8 MPa.
  • the total amount of TFE supplied to A / C was 0.17 kg (1.65 mol).
  • 244cc was obtained by the following method.
  • a gas phase reactor made of SUS316, diameter 25 mm, length 30 cm
  • activated carbon pellets 15 g supporting palladium at a ratio of 2.0 mass%
  • the temperature was raised to 130 ° C. while flowing nitrogen (N 2 ) gas (500 NmL / min).
  • N 2 nitrogen
  • the catalyst was dried until the moisture in the gas obtained from the outlet of the reaction tube became 20 ppm or less.
  • the supply of nitrogen was stopped, the reaction tube was heated to 200 ° C. while supplying hydrogen (180 mL / min), and then 224ca (0.44 g / min) was supplied.
  • the crude gas obtained from the outlet of the reaction tube was washed with water, acid and moisture were removed through an alkali washing tower and molecular sieve 5A, and then collected in a cold trap.
  • the conversion of 224ca was 98%, and 1,3-dichloro-1,1,2,2-tetrafluoropropane (HCFC-234cc) had a selectivity of 24%.
  • 244 cc was obtained with a selectivity of 70%.
  • a total of 500 g (2.27 mol) of 224ca was reacted above to give 298 g of crude product.
  • the obtained crude product was subjected to normal pressure rectification in a 25-stage rectification column to obtain a total of 200 g of 244 cc.
  • a / C was placed in an oil bath and the temperature was raised to 180 ° C., which is the reaction temperature.
  • the temperature was raised for just over 1 hour, and the stirring blade was rotated at 300 rpm during the temperature rise and during the reaction.
  • the stirring blades used were two paddle blades.
  • the temperature of the oil bath was lowered and cooled to room temperature. During the reaction, the reaction was carried out in a sealed state without purging.
  • reaction solution was sampled from the insertion tube into a high pressure syringe and analyzed by GC.
  • the composition analysis of 244cc and 1243yc which is a de-ClF form was performed by GC analysis, and the conversion and selectivity were calculated.
  • the conversion rate of 244 cc was 79.2%
  • the selectivity of 1243yc was 98.6%
  • 1243yc could be obtained in a very high yield of 78.1%.
  • the reaction tube was installed in a water bath, and the temperature was raised to 75 ° C., which is the reaction temperature. The temperature was raised in less than 10 minutes. After raising the temperature to 75 ° C., the temperature was controlled at ⁇ 1 ° C. and mixed for 4 hours. During the reaction, since the deClF form is a low boiling point compound, the reaction pressure gradually increases, but the reaction was carried out in a sealed state without purging. After completion of the reaction, the temperature of the water bath was lowered and cooled to room temperature. After the temperature dropped to room temperature, the reaction solution was sampled from the insertion tube into a high pressure syringe and analyzed by GC.
  • the composition analysis of 224cb and 1224ye which is a de-ClF form was performed by GC analysis, and the conversion and selectivity were calculated.
  • the conversion rate of 225cb was 19.2%
  • the selectivity of 1224ye was 1.70%
  • the yield was as low as 0.33%. It is considered that the conversion rate did not increase because it was a reaction tube test without a stirring mechanism.
  • the selectivity was very low, there were two or more deClF routes, and in the reaction test, solvent-derived desorption as a reaction byproduct.
  • a large amount of Cl—H substitution product such as 1-chloro-1,2,2,3,3-pentafluoropropane (CF 2 H—CF 2 —CClFH, HCFC-235ca) was produced.
  • a / C was installed in the water bath, and it heated up to 75 degreeC which is reaction temperature.
  • the temperature was raised in less than 1 hour, and the stirring blade was rotated at 300 rpm during the temperature rise and during the reaction.
  • the stirring blades used were two paddle blades.
  • the temperature was controlled at ⁇ 1 ° C. and stirred for 5 hours.
  • the deClF form is a low-boiling compound (boiling point of about 15 ° C.), so the reaction pressure gradually increases, but the reaction was carried out in a sealed state without purging.
  • the composition of 225cb and 1224ye which is a de-ClF form was analyzed by GC analysis, and the conversion and selectivity were calculated. As a result, the conversion rate of 225cb was 3.6%, the selectivity of 1224ye was 30.8%, and the yield was 1.1%, which was a very low yield.
  • Examples 3 to 9 1224yd was produced in the same manner as in Example 1 except that the conditions described in Tables 1 and 2 below were changed.
  • Example 10 Production of 1234yc (1,1,2,3-tetrafluoropropene) by de-ClF of 235 cc (1-chloro-1,1,2,2,3-pentafluoropropane) [Production of 235 cc ]
  • 235 cc (1-chloro-1,1,2,2,3-pentafluoropropane)
  • 1550 g of a crude product containing 16.4% by mass of 235 cc was obtained.
  • the obtained crude product was subjected to normal pressure rectification in a 25-stage rectification column to obtain a total of 200 g of 235 cc.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production permettant d'obtenir de manière efficace un propène contenant du fluor ayant une structure -CF= avec un rendement élevé par l'utilisation d'un propane contenant du fluor ayant une structure -CF2- dans chaque molécule en tant que matériau de départ. L'invention concerne un procédé de production d'un propène contenant du fluor, au moyen duquel un propène contenant du fluor représenté par la formule (B) est obtenu par soumission d'un propane contenant du chlore contenant du fluor représenté par la formule (A) à une réaction de déchloration-défluoration en présence d'un agent réducteur composé d'au moins un élément choisi parmi des métaux alcalino-terreux et des métaux de transition. Formule (A) : CY3-CF2-CClX2, Formule (B) : CY3-CF=CX2, dans la formule (A), chacune des deux fractions X représente indépendamment F, Cl ou H ; et chacune des trois fractions Y représente indépendamment F ou H, à l'exclusion des cas où les deux fractions X représentent H. Dans la formule (B), les fractions X et Y sont telles que définies dans la formule (A).
PCT/JP2019/019762 2018-05-28 2019-05-17 Procédé de production d'un propène contenant du fluor WO2019230456A1 (fr)

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WO2022107020A1 (fr) * 2020-11-23 2022-05-27 3M Innovative Properties Company Composition de revêtement comprenant un fluoropolymère durcissable et un hydrofluorochloropropène, et fluoroélastomères issus de celle-ci

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WO2022107020A1 (fr) * 2020-11-23 2022-05-27 3M Innovative Properties Company Composition de revêtement comprenant un fluoropolymère durcissable et un hydrofluorochloropropène, et fluoroélastomères issus de celle-ci

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