WO2019203318A1 - Procédé de production de fluorooléfine - Google Patents

Procédé de production de fluorooléfine Download PDF

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WO2019203318A1
WO2019203318A1 PCT/JP2019/016677 JP2019016677W WO2019203318A1 WO 2019203318 A1 WO2019203318 A1 WO 2019203318A1 JP 2019016677 W JP2019016677 W JP 2019016677W WO 2019203318 A1 WO2019203318 A1 WO 2019203318A1
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production method
reaction
hydrofluorocarbon
hydrochlorofluorocarbon
water
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PCT/JP2019/016677
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English (en)
Japanese (ja)
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英史 塩田
古田　昇二
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Ａｇｃ株式会社
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for efficiently producing a fluoroolefin, specifically, a hydrofluoroolefin, a perfluoroolefin, a hydrochlorofluoroolefin or a chlorofluoroolefin in a liquid phase.
  • hydrofluorocarbons and hydrochlorofluorocarbons have been used for cleaning agents, refrigerants, foaming agents, solvents, aerosols and the like.
  • these compounds may cause global warming. Therefore, halogenated olefins are attracting attention as compounds having a small global warming potential.
  • hydrofluorocarbons or hydrochlorofluorocarbons having a structure in which hydrogen atoms, fluorine atoms or chlorine atoms are bonded to two adjacent carbon atoms in the molecule are dehydrochlorinated.
  • a reaction for dehydrofluorination is known.
  • Patent Document 1 discloses a reaction in which XCF 2 CF 2 CHClY is dehydrofluorinated to obtain XCF 2 CF ⁇ CClY (X and Y are fluorine atoms or chlorine atoms), and 1,1 1,2,2,3,3-hexafluoro-3-chloropropane is dehydrochlorinated to give hexafluoropropene.
  • Patent Document 2 describes a method for producing 1-chloro-2,3,3-trifluoropropene by dehydrofluorinating 1-chloro-2,2,3,3-tetrafluoropropane.
  • Patent Document 3 1,1-dichloro-2,2,3,3,3-pentafluoropropane is subjected to dehydrofluorination to produce 1,1-dichloro-2,3,3,3-tetra
  • a method for obtaining fluoropropene is described.
  • the present invention has been made from the above viewpoint, and is an efficient fluoroolefin in a liquid phase from hydrofluorocarbon or hydrochlorofluorocarbon, specifically, hydrofluoroolefin, perfluoroolefin, hydrochlorofluoroolefin or chlorofluoroolefin. It aims at providing the method of manufacturing.
  • HFC Hydrofluorocarbon
  • hydrochloro having 3 to 7 carbon atoms and having a structure in which a hydrogen atom and a fluorine atom or a chlorine atom are bonded to two adjacent carbon atoms, respectively.
  • Fluorocarbon (HCFC) is brought into contact with an alkaline aqueous solution in the liquid phase in the presence of a phase transfer catalyst and a water-soluble organic solvent capable of dissolving HFC or HCFC (hereinafter also referred to as water-soluble organic solvent (S)).
  • S water-soluble organic solvent
  • the HFC or HCFC is dehydrochlorinated or dehydrofluorinated to at least one selected from hydrofluoroolefin (HFO), perfluoroolefin (PFO), hydrochlorofluoroolefin (HCFO) and chlorofluoroolefin (CFO)
  • HFO hydrofluoroolefin
  • PFO perfluoroolefin
  • HCFO hydrochlorofluoroolefin
  • CFO chlorofluoroolefin
  • Ra [4 ⁇ ( ⁇ D 1 - ⁇ D 2) 2 + ( ⁇ P 1 - ⁇ P 2) 2 + ( ⁇ H 1 - ⁇ H 2) 2] 0.5
  • ⁇ D 1, ⁇ P 1 and delta] H 1 respectively, in the Hansen solubility parameters of the water-soluble organic solvent, shows the dispersion term, polarity term and hydrogen bond
  • [delta] D 2 [delta] P 2 and delta] H 2 represents a dispersion term, a polar term and a hydrogen bond term in the Hansen solubility parameter of the hydrofluorocarbon or hydrochlorofluorocarbon, respectively, and the unit is (MPa) 1/2 .
  • phase transfer catalyst is tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, or methyltri-n-octylammonium chloride.
  • Method [10] The production method according to any one of [1] to [9], wherein the hydrofluorocarbon or hydrochlorofluorocarbon is monochlorotetrafluoropropane, and the fluoroolefin is tetrafluoropropene.
  • the monochlorotetrafluoropropane is 2-chloro-1,1,1,2-tetrafluoropropane and / or 3-chloro-1,1,1,2-tetrafluoropropane, and the tetrafluoropropene is The production method according to [10], which is 2,3,3,3-tetrafluoropropene.
  • the dichlorotetrafluoropropane is 2,3-dichloro-1,1,1,2-tetrafluoropropane and / or 3,3-dichloro-1,1,1,2-tetrafluoropropane,
  • a fluoroolefin specifically, a hydrofluoroolefin, a perfluoroolefin, a hydrochlorofluoroolefin, or a chlorofluoroolefin can be efficiently produced in a liquid phase from hydrofluorocarbon or hydrochlorofluorocarbon.
  • a reactor smaller than a gas phase reaction can be employed, which is industrially advantageous.
  • halogenated hydrocarbon an abbreviation of the compound is described in parentheses after the compound name, and the abbreviation is used instead of the compound name as necessary.
  • abbreviations only numbers after the hyphen (-) and lower-case alphabetic characters (for example, "1224yd” in “HCFO-1224yd") may be used.
  • E) attached to the names of compounds having geometric isomers and their abbreviations indicate E form (trans form), and (Z) indicates Z form (cis form).
  • the names and abbreviations are generic names including E-form, Z-form, and a mixture of E-form and Z-form.
  • reaction represented by reaction formula (1) is referred to as reaction (1).
  • reaction (1) The same applies to reactions represented by other formulas.
  • the compound represented by formula (A) is referred to as compound (A).
  • compound (A) The same applies to compounds represented by other formulas.
  • Each of “ ⁇ ” representing a numerical range includes an upper limit value and a lower limit value.
  • HSP The “Hansen solubility parameter of a compound” is composed of a dispersion term, a polar term and a hydrogen bond term.
  • HSP is a literature value or a value estimated by computer software (Hansen Solubility Parameters in Practice (HSPiP) version 4) from the chemical structure of a compound.
  • HSP of a mixture containing two or more compounds is calculated as a vector sum of values obtained by multiplying the HSP of each compound by the volume ratio of each compound to the entire mixture.
  • Pressure represents “gauge pressure” unless otherwise specified.
  • reaction to which the production method of the present invention can be applied is specifically a reaction shown in the following reaction formula (1).
  • the above-mentioned HFC or HCFC which is a starting material (raw material) is represented by the formula (A)
  • the target product which is HFO, PFO, HCFO or CFO is represented by the formula (B).
  • Formula (C) is hydrogen chloride or hydrogen fluoride.
  • X 1 and X 2 are each independently a hydrogen atom, and the other is a fluorine atom or a chlorine atom.
  • Y 1 and Y 2 are each independently a hydrogen atom, a fluorine atom or a chlorine atom.
  • R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a chlorine atom or an aliphatic saturated hydrocarbon group having 1 to 5 carbon atoms (however, part or all of the hydrogen atoms are chlorine atoms or fluorine atoms) And the total number of carbon atoms of R 1 and R 2 is 1-5. At least one of Y 1 , Y 2 , R 1 and R 2 is a fluorine atom.
  • reaction (1) when compound (A) is brought into contact with an alkaline aqueous solution in the liquid phase, as shown in reaction (1), hydrogen chloride or hydrogen fluoride is eliminated from compound (A) to obtain compound (B).
  • This reaction is performed in a two-phase state of an organic phase mainly composed of the compound (A) and an aqueous phase mainly composed of an alkaline aqueous solution.
  • the stirring conditions and the device are devised, and the phase transfer catalyst is used to promote the reaction.
  • increasing the reaction speed and improving the productivity It was not easy.
  • the present inventors perform contact between the compound (A) and the aqueous alkali solution in the presence of a phase transfer catalyst and the water-soluble organic solvent (S), thereby providing the water-soluble organic solvent (S).
  • the compound (B) can be produced more efficiently by promoting the action of the phase transfer catalyst, and has led to the completion of the present invention.
  • Formula (1-1) is a compound represented by 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca) and / or 1,1-dichloro-1,2,3,3,3
  • Formula (1-2) is 2,3,3-trichloro-1,1,1,2-tetrafluoropropane (HCFC-224ba) and / or 1,1,1-trichloro-2,3,3,3 A reaction formula for obtaining CFO-1214ya from tetrafluoropropane (HCFC-224eb) by deHCl.
  • Formula (2-1) represents 1,1,1,2,2,3,3-heptafluoropropane (HFC-227ca) and / or 1,1,1,2,3,3,3-heptafluoropropane.
  • This is a reaction formula for obtaining hexafluoropropene (PFO-1216) from (HFC-227ea) by deHF.
  • Formula (2-2) is 2-chloro-1,1,1,2,3,3-hexafluoropropane (HCFC-226ba) and / or 1-chloro-1,1,2,3,3,3
  • Formula (3-1) represents 3-chloro-1,1,1,2,2-pentafluoropropane (HCFC-235cb) and / or 3-chloro-1,1,1,2,3-pentafluoropropane
  • deHF from (HCFC-235ea) (Z) -1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd (Z)) and / or (E) -1-chloro-2,3 , 3,3-tetrafluoropropene (HCFO-1224yd (E)).
  • Formula (3-2) represents 2,3-dichloro-1,1,1,2-tetrafluoropropane (HCFC-234bb) and / or 3,3-dichloro-1,1,1,2-tetrafluoropropane This is a reaction formula for obtaining HCFO-1224yd (Z) and / or HCFO-1224yd (E) from (HCFC-234ea) by removing HCl.
  • Formula (4-1) is a compound represented by 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and / or 2-chloro-1,1,1,3-tetrafluoropropane (HCFC-244db).
  • HCFC-244bb 2-chloro-1,1,1,3-tetrafluoropropane
  • HCFC-244db 2-chloro-3,3,3-trifluoropropene
  • Formula (4-2) is a compound represented by 2,2-dichloro-1,1,1-trifluoropropane (HCFC-243xb) and / or 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db). Is a reaction formula for obtaining HCFO-1233xf from HCl by dehydrochlorination.
  • Formula (5-1) is a compound represented by the following formula: 3-chloro-1,1,2,2-tetrafluoropropane (HCFC-244ca) and / or 1-chloro-1,2,3,3-tetrafluoropropane (HCFC-244ea) ) To (Z) -1-chloro-2,3,3-trifluoropropene (HCFO-1233yd (Z)) and / or (E) -1-chloro-2,3,3-trifluoropropene This is a reaction formula for obtaining (HCFO-1233yd (E)).
  • Formula (5-2) is a compound represented by 2,3-dichloro-1,1,2-trifluoropropane (HCFC-243ba) and / or 1,1-dichloro-2,3,3-trifluoropropane (HCFC-243eb).
  • Formula (6-1) is a compound represented by the following formula: 3-chloro-1,1,1,2-tetrafluoropropane (HCFC-244eb) and / or 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa).
  • HCFC-244eb 3-chloro-1,1,1,2-tetrafluoropropane
  • HCFC-244fa 3-chloro-1,1,1,3-tetrafluoropropane
  • Formula (6-2) is a compound represented by 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) and / or 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa).
  • Formula (7-1) is obtained by removing HF from 1,1,1,2,2-pentafluoropropane (HFC-245cb) and / or 1,1,1,2,3-pentafluoropropane (HFC-245eb). Is a reaction formula for obtaining 2,3,3,3-tetrafluoropropene (HFO-1234yf).
  • Formula (7-2) is a compound represented by 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and / or 3-chloro-1,1,1,2-tetrafluoropropane (HCFC-244eb). ) From HCI-1234yf by deHCl.
  • Formula (8-1) is obtained by removing HF from 1,1,1,2,3-pentafluoropropane (HFC-245eb) and / or 1,1,1,3,3-pentafluoropropane (HFC-245fa).
  • Is a reaction formula to obtain Formula (8-2) is a compound represented by 2-chloro-1,1,1,3-tetrafluoropropane (HCFC-244db) and / or 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa).
  • Formula (9-1) represents 2,3-dichloro-1,1,1,2-tetrafluoropropane (HCFC-234bb) and / or 2,3-dichloro-1,1,1,3-tetrafluoropropane (HC) -234da) to (Z) -1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (Z)) and / or (E) -1,2-dichloro-3 , 3,3-trifluoropropene (HCFO-1223xd (E)).
  • Formula (9-2) represents 2,2,3-trichloro-1,1,1-trifluoropropane (HCFC-233ab) and / or 2,3,3-trichloro-1,1,1-trifluoropropane This is a reaction formula for obtaining HCFO-1223xd (Z) and / or HCFO-1223xd (E) from (HCFC-233da) by de-HCl.
  • Formula (10-1) is represented by 1,1,1,2,2,3-hexafluoropropane (HFC-236cb) and / or 1,1,1,2,3,3-hexafluoropropane (HFC-236eb).
  • HFC-236cb 1,1,1,2,3,3-hexafluoropropane
  • HFC-236eb 1,1,1,2,3,3-hexafluoropropane
  • Formula (10-2) is 2-chloro-1,1,1,2,3-pentafluoropropane (HCFC-235bb) and / or 3-chloro-1,1,1,2,3-pentafluoropropane This is a reaction formula for obtaining HFO-1225ye (Z) and / or HFO-1225ye (E) by removing HCl from (HCFC-235ea).
  • Formula (11-1) can be obtained by removing HF from 1,1,1,2-tetrafluoropropane (HFC-254eb) and / or 1,1,1,3-tetrafluoropropane (HFC-254fb) to form 3,3 , 3-trifluoropropene (HFO-1243zf) is obtained.
  • Formula (11-2) is obtained by removing HCl from 2-chloro-1,1,1-trifluoropropane (HCFC-253db) and / or 3-chloro-1,1,1-trifluoropropane (HCFC-244eb). Is a reaction formula for obtaining HFO-1243zf.
  • Formula (12-1) is obtained by removing 3,1,3-difluoropropene (HFC-263eb) and / or 1,1,3-trifluoropropane (HFC-263fa) by deHF. This is a reaction formula to obtain HFO-1252zf).
  • Formula (12-2) yields HFO-1252zf from 2-chloro-1,1-difluoropropane (HCFC-262db) and / or 3-chloro-1,1-difluoropropane (HCFC-262fa) by de-HCl It is a reaction formula.
  • Formula (13-1) is obtained by removing HF from 1,1,1,2,4,4-heptafluorobutane (HFC-347mef) and (Z) -1,1,1,4,4,4- Reaction to obtain hexafluoro-2-butene (HFO-1336mzz (Z)) and / or (E) -1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz (E)) It is a formula.
  • Formula (13-2) is obtained by removing HFO-1336mzz (Z) or HFO-1336mzz (E) from 2-chloro-1,1,1,4,4,4-hexafluorobutane (HCFC-346mdf) by removing HCl. It is the reaction formula to be obtained.
  • Formula (14-1) is a compound represented by the following formula: 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane (HCFC-448occc) and / or 5-chloro-1,1,2,2 (Z) -1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HC), 3,4,5-octafluoropentane (HCFC-448 pcce) by deHF Reaction formula to obtain HCFO-1437 dycc (Z)) and / or (E) -1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437 dycc (E)) It is.
  • Formula (14-2) is a compound represented by 4,5-dichloro-1,1,2,2,3,3,4-heptafluoropentane (HCFC-447 obscc) and / or 5,5-dichloro-1,1,2, , 2,3,3,4-heptafluoropentane (HCFC-447necc) to remove HCFO-1437 dycc (Z) and / or HCFO-1437 dycc (E) by removing HCl.
  • HCFC-447 obscc 4,5-dichloro-1,1,2,2,3,3,4-heptafluoropentane
  • HCFC-447necc 5,5-dichloro-1,1,2, , 2,3,3,4-heptafluoropentane
  • Formula (15-1) is a compound represented by the following formula: 3-chloro-1,1,1,2,2,3-hexafluoropropane (HCFC-226ca) and / or 1-chloro-1,1,2,3,3,3 By deHF from hexafluoropropane (HCFC-226ea) (Z) -1-chloro-1,2,3,3,3-pentafluoropropene (CFO-1215yb (Z)) and / or (E) -1 This is a reaction formula for obtaining -chloro-1,2,3,3,3-pentafluoropropene (CFO-1215yb (E)).
  • Formula (15-2) is a compound represented by 2,3-dichloro-1,1,1,2,3-pentafluoropropane (HCFC-225ba) and / or 1,1-dichloro-1,2,3,3,3.
  • the reaction in which the production method of the present invention is suitably used is a reaction in which tetrafluoropropene is obtained from monochlorotetrafluoropropane by deHCl from the point that the reaction rate can be improved and the reaction can be carried out efficiently
  • a reaction for obtaining monochlorotetrafluoropropene from dichlorotetrafluoropropane by dehydrochlorination is mentioned.
  • Examples of the reaction for obtaining tetrafluoropropene from monochlorotetrafluoropropane by removing HCl include 244bb and / or 244eb of formula (7-2) to obtain 1234yf by removing HCl, 244db and / or 244fa of formula (8-2)
  • the reaction to obtain 1234ze (Z) and / or 1234ze (E) by dehydrochlorination from H More preferred is a reaction of obtaining 1234yf from 244bb and / or 244eb of the formula (7-2) by deHCl.
  • the effect of the present invention is great particularly when the raw material includes a compound having a CH 3 group such as 244bb and the elimination of H from the CH 3 group of the compound is required. Therefore, a high effect can be expected in the reaction of obtaining 1234yf from 244bb by deHCl.
  • the compound (A) is in a liquid phase as an organic phase and is in physical contact with an alkaline aqueous solution, more specifically, by contacting with a base in the alkaline aqueous solution.
  • DeHF or deHCl reaction occurs to produce compound (B).
  • the contact between the compound (A) and the alkaline aqueous solution is carried out in the liquid phase in the presence of a phase transfer catalyst and a water-soluble organic solvent (S).
  • the contact according to the production method of the present invention is usually performed in a reactor.
  • the method for obtaining the compound (A) is not particularly limited. You may manufacture by a well-known method and may use a commercial item.
  • 244bb and / or 244eb in the reaction (7-2) to which the present invention is preferably applied can be produced, for example, by a chlorination reaction in which 254eb is reacted with chlorine.
  • 234bb and / or 234ea in the reaction (3-2) can be produced, for example, by further chlorinating 244bb and / or 244eb obtained in the chlorination reaction of 254eb.
  • the compound (A) may be introduced into the reactor in the form of a mixture containing the 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 of the compound (A) having a purity of 85% by mass or more, preferably 90% by mass or more, particularly preferably 95% by mass or more can be used in the production method of the present invention.
  • the alkaline aqueous solution used in the production method of the present invention refers to an aqueous solution in which a base is dissolved in water.
  • the base is not particularly limited as long as the above reaction (1) can be performed.
  • the base preferably contains at least one selected from the group consisting of metal hydroxides, metal oxides and metal carbonates.
  • examples include alkaline earth metal hydroxides and alkali metal hydroxides.
  • examples of the alkaline earth metal hydroxide include magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.
  • examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
  • examples of the metal constituting the metal oxide include an alkali metal element, an alkaline earth metal element, a transition metal element, a Group 12 metal element, and a Group 13 metal element.
  • alkali metal elements, alkaline earth metal elements, Group 6 metal elements, Group 8 metal elements, Group 10 metal elements, Group 12 metal elements, or Group 13 metal elements are preferable, and sodium, calcium, chromium More preferred are iron, zinc, or aluminum.
  • the metal oxide may be an oxide containing one kind of metal or a composite oxide of two or more kinds of metals.
  • the metal oxide sodium oxide, calcium oxide, chromium oxide (chromia), aluminum oxide (alumina), zinc oxide, or the like is preferable from the viewpoint of reaction time and reaction yield, and alumina or chromia is more preferable.
  • examples include alkaline earth metal carbonates and alkali metal carbonates.
  • alkaline earth metal carbonate include carbonates of metals such as beryllium, magnesium, calcium, strontium, barium, and radium.
  • alkali metal carbonate include metal carbonates such as lithium, sodium, potassium, rubidium, cesium, and francium.
  • the base used in the production method of the present invention is preferably a metal hydroxide from the viewpoint of reaction time and reaction yield, and particularly preferably at least one selected from the group consisting of potassium hydroxide and sodium hydroxide.
  • a metal hydroxide may be used individually by 1 type and may use 2 or more types together.
  • the content of the base in the alkaline aqueous solution is preferably such that the ratio (unit%) of the mass of the base to the total amount (mass) of the alkaline aqueous solution is 0.5 to 48% by mass from the viewpoint of the reaction rate, and 20 to 45% by mass. % Is more preferable, and 30 to 40% by mass is further preferable. If the amount of base is less than the above range, a sufficient reaction rate may not be obtained. On the other hand, when the amount of the base exceeds the above range, the amount of by-products generated increases, and the selectivity for the target substance (compound (B)) may decrease.
  • the amount of base used in the production method of the present invention depends on the type of reaction (1).
  • the amount of base relative to 1 mol of 244bb and / or 244eb is from the viewpoint of improving the conversion of 244bb and / or 244eb and the selectivity of 1234yf. 0.2 to 3.0 mol is preferable, and 0.5 to 2.5 mol is more preferable.
  • the conversion rate of 234bb and / or 234ea and 1224yd (Z) and / or 1224yd (E) from 234bb and / or 234ea by deHCl the conversion rate of 234bb and / or 234ea and 1224yd (Z) and / or 1224yd (E)
  • the amount of the base relative to 1 mol of 234bb and / or 234ea is preferably 0.2 to 3.0 mol, and more preferably 0.5 to 2.5 mol.
  • the reaction solution is composed of an organic phase mainly composed of the compound (A) and an aqueous phase composed of an alkaline aqueous solution.
  • the phase transfer catalyst is present both in the organic phase and in the alkaline aqueous solution, and promotes the dehalogenation reaction by contact of the compound (A) with the alkaline aqueous solution.
  • phase transfer catalyst examples include quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, sulfonium salts, crown ethers, etc., and are quaternary from the viewpoint of industrial availability, price, and ease of handling. Ammonium salts are preferred.
  • TBAC tetra-n-butylammonium chloride
  • TBAB tetra-n-butylammonium bromide
  • TOMAC methyltri-n-octylammonium chloride
  • TBAB tetra-n-butylammonium bromide
  • TOMAC methyltri-n-octylammonium chloride
  • TBAB tetra-n-butylammonium chloride
  • TBAC tetra-n-butylammonium bromide
  • TBAB tetra-n-butylammonium bromide
  • the amount of the phase transfer catalyst used in the production method of the present invention is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, more preferably 0.01 to 100 parts by weight of the compound (A). More preferred is 3 parts by mass. If the amount of the phase transfer catalyst is too small, a sufficient reaction rate may not be obtained. Even if it is used in a large amount, the reaction promoting effect according to the amount used cannot be obtained, which is disadvantageous in terms of cost.
  • the water-soluble organic solvent (S) is water-soluble and can dissolve the compound (A).
  • the water-solubility in the water-soluble organic solvent (S) means that the water-soluble organic solvent (S) and pure water are mixed at an arbitrary mixing ratio at 25 ° C. without causing phase separation or turbidity. A property that dissolves uniformly.
  • the water-soluble organic solvent (S) can dissolve the compound (A) at 25 ° C. with respect to the compound (A) in such an amount that the water-soluble organic solvent (S) is 20% by mass. When A) and a water-soluble organic solvent (S) are mixed, they are dissolved uniformly without causing phase separation or turbidity.
  • the water-soluble organic solvent (S) is present both in the organic phase and in the alkaline aqueous solution as in the phase transfer catalyst, and has a function of further enhancing the action of promoting the dehalogenation reaction of the compound (A) in the phase transfer catalyst.
  • water-soluble organic solvent (S) for example, a compound capable of dissolving the compound (A) from a water-soluble alcohol, ketone, ether, ester or the like is appropriately selected and used depending on the type of the compound (A). .
  • water-soluble alcohol examples include methanol, ethanol, propan-1-ol, butan-1-ol, propan-2-ol, butan-2-ol, 2-methylpropan-2-ol, and 2-methylbutane-
  • water-soluble ketones such as 2-ol include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone.
  • water-soluble ethers examples include tetraethylene glycol dimethyl ether (hereinafter also referred to as “tetraglyme”), chain ethers such as dimethyl ether, ethyl methyl ether, diethyl ether, and ethylene oxide, and cyclic ethers such as tetrahydrofuran, furan, and crown ethers.
  • tetraglyme tetraethylene glycol dimethyl ether
  • chain ethers such as dimethyl ether, ethyl methyl ether, diethyl ether, and ethylene oxide
  • cyclic ethers such as tetrahydrofuran, furan, and crown ethers.
  • water-soluble esters examples include methyl acetate and methyl formate.
  • the water-soluble organic solvent (S) has a property of dissolving the compound (A) in addition to water solubility.
  • the water-soluble organic solvent (S) is a water-soluble organic solvent (S) represented by the following formula (I) based on the Hansen solubility parameter from the viewpoint of further enhancing the action of the phase transfer catalyst in the dehalogenation reaction of the compound (A).
  • the compound (A) are preferably 25.0 or less, more preferably 23.0 or less, and particularly preferably 22.0 or less.
  • Ra [4 ⁇ ( ⁇ D 1 - ⁇ D 2) 2 + ( ⁇ P 1 - ⁇ P 2) 2 + ( ⁇ H 1 - ⁇ H 2) 2] 0.5 (I)
  • Each formula (I), ⁇ D 1, ⁇ P 1 and delta] H 1 is the Hansen solubility parameter of the water-soluble organic solvent (S), dispersion term, the polarity term and hydrogen bond, [delta] D 2, [delta] P 2 and delta] H 2 is Each represents a dispersion term, a polar term and a hydrogen bonding term in the Hansen solubility parameter of the compound (A), and the unit is (MPa) 1/2 .
  • the interaction distance (Ra) is preferably small, and the lower limit is not particularly limited.
  • methanol, acetone, tetraglyme, and tetrahydrofuran have an interaction distance (Ra) of 25.0 or less for all of 244bb, 244eb, 234bb, and 234ea.
  • Ra interaction distance
  • It can be preferably used as the water-soluble organic solvent (S).
  • a preferred combination of the compound (A) and the water-soluble organic solvent (S) other than those shown in Table 1 can be selected using the interaction distance (Ra) as an index.
  • the amount of the water-soluble organic solvent (S) used in the production method of the present invention is preferably 1 to 100 parts by weight, more preferably 3 to 80 parts by weight with respect to 100 parts by weight of the compound (A). Part by mass is more preferable. If the amount of the water-soluble organic solvent (S) is too small, a sufficient reaction rate may not be obtained, and even if it is used in a large amount, a reaction promoting effect according to the amount of use cannot be obtained. It is disadvantageous in terms.
  • reaction conditions other than those described above in the reaction (1) for example, temperature, pressure, etc., can be generally the same as the reaction conditions when the alkaline aqueous solution and the compound (A) are contacted in the liquid phase to cause deHF or deHCl reaction. .
  • the reaction temperature that is, the temperature in the reactor is preferably 40 to 120 ° C, more preferably 50 to 110 ° C.
  • the reaction temperature is preferably 60 to 120 ° C, more preferably 80 to 110 ° C.
  • the reaction temperature is preferably 40 to 80 ° C., more preferably 50 to 70 ° C.
  • the pressure in the reactor during the reaction is preferably 0.00 to 10.00 MPa, more preferably 0.05 to 5.00 MPa, and more preferably 0.15 to More preferred is 2.00 MPa.
  • the pressure in the reactor is preferably equal to or higher than the vapor pressure of 244bb and / or 244eb at the reaction temperature.
  • the reaction temperature that is, the temperature in the reactor is preferably 10 to 90 ° C., and 20 to 80 ° C. is more preferable.
  • the pressure in the reactor during the reaction is preferably 0.00 to 5.00 MPa, more preferably 0.02 to 2.00 MPa, and further preferably 0.05 to 1.00 MPa.
  • a stirring blade is installed in a batch type, semi-continuous type or continuous type reactor, and it is generated by stirring it. It is preferable.
  • the stirring blade include a 4-paddle blade, an anchor blade, a gate blade, a 3-propeller, a ribbon blade, and a 6-turbine blade.
  • the production method of the present invention is usually carried out by introducing predetermined amounts of the compound (A), the aqueous alkali solution, the phase transfer catalyst and the water-soluble organic solvent (S) into the reactor.
  • the material of the reactor is not particularly limited as long as it is inert and corrosion-resistant material such as compound (A), alkaline aqueous solution, phase transfer catalyst, water-soluble organic solvent (S) and reaction liquid components including reaction products.
  • glass, iron, nickel, an alloy such as stainless steel mainly containing iron, and the like can be given.
  • the reaction in the present invention may be carried out batchwise, semi-continuously or continuously.
  • the reaction solution is left to separate into an organic phase and an aqueous phase.
  • the organic phase may contain unreacted compound (A), by-products, phase transfer catalyst, water-soluble organic solvent (S) and the like in addition to the target product compound (B).
  • a separation and purification method such as general distillation.
  • the compound (A) can be concentrated by distillation and recycled as the raw material of the present invention.
  • the aqueous phase separated from the organic phase can be reused by taking out only this amount and adding a base so as to obtain an appropriate concentration again.
  • the phase transfer catalyst and the water-soluble organic solvent (S) may be separated from the organic phase or the aqueous phase, but if they remain in the compound (A) or the aqueous phase, they can be reused while being contained. It is also possible to do.
  • the purified compound (B) containing the compound (B) with high purity can be obtained by separating and purifying the compound (B) obtained by the production method of the present invention as described above. If the purified compound (B) thus obtained contains an acid content such as HF or HCl, or an impurity such as water or oxygen, the equipment will corrode during its use, and the stability of the compound (B) will decrease. There is a risk of. Therefore, it is preferable to remove these impurities by a conventionally known method to such an extent that there is no problem with corrosion and stability.
  • Examples 1 to 4 are examples, and examples 5 and 6 are comparative examples.
  • reaction solution was neutralized by mixing with a 20% by mass aqueous solution of potassium hydrogen carbonate, and then a liquid separation operation was performed. After standing, the reaction composition was recovered from the separated lower layer, and 244bb was obtained by distillation.
  • TBAB Tetra-n-butylammonium bromide
  • Example 2 1234yf was produced in the same manner except that acetone, tetraglyme, or tetrahydrofuran was used instead of methanol.
  • the results of collecting the reaction composition and performing GC analysis are shown in Table 2.
  • Example 5 1234yf was produced in the same manner as in Example 1 except that methanol was not used. The results of collecting the reaction composition and performing GC analysis are shown in Table 2.
  • Example 6 In Example 1, 1234yf was produced in the same manner except that TBAB was not used. The results of collecting the reaction composition and performing GC analysis are shown in Table 2.

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

Abstract

L'invention concerne un procédé de production, en phase liquide, d'une fluorooléfine à partir d'hydrofluorocarbure (HFC) ou d'hydrochlorofluorocarbone (HCFC) avec une efficacité élevée. L'invention concerne un procédé de production d'une fluorooléfine, le procédé comprenant les étapes consistant à mettre en contact, en phase liquide, du HFC ou du HCFC, ayant chacun de 3 à 7 atomes de carbone et ayant également, dans leur molécule, une structure tel qu'un atome d'hydrogène et un atome de fluor ou de chlore liés respectivement à deux atomes de carbone adjacents, avec une solution alcaline aqueuse en présence d'un catalyseur de transfert de phase et d'un solvant organique soluble dans l'eau capable de dissoudre du HFC ou du HCFC pour provoquer l'élimination du chlorure d'hydrogène ou du fluorure d'hydrogène à partir du HFC ou du HCFC, ce qui permet de produire une hydrofluorooléfine, une perfluorooléfine, une hydrochlorofluorooléfine ou une chlorofluorooléfine.
PCT/JP2019/016677 2018-04-19 2019-04-18 Procédé de production de fluorooléfine WO2019203318A1 (fr)

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WO2020247423A1 (fr) 2019-06-04 2020-12-10 The Chemours Company Fc, Llc Compositions de 2-chloro-3,3,3-trifluoropropène (1233xf) et leurs procédés de fabrication et d'utilisation
WO2021132390A1 (fr) * 2019-12-26 2021-07-01 Ａｇｃ株式会社 Procédé de production de 1-chloro-2,3,3-trifluoropropène
CN115557827A (zh) * 2022-08-29 2023-01-03 西安近代化学研究所 一种3-氯-3,3-二氟丙烯的制备方法
TWI798875B (zh) * 2020-10-15 2023-04-11 日商昭和電工股份有限公司 蝕刻氣體及其製造方法、以及、蝕刻方法、半導體元件之製造方法

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JP2013528585A (ja) * 2010-04-29 2013-07-11 ハネウェル・インターナショナル・インコーポレーテッド テトラフルオロプロペンの製造方法
WO2017018412A1 (fr) * 2015-07-27 2017-02-02 旭硝子株式会社 Procédé de production de 1-chloro-2,3,3-trifluoropropène
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JP2012526146A (ja) * 2009-05-08 2012-10-25 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ヒドロフルオロオレフィン生成においてモノフルオロ酢酸塩の量を低減する方法
JP2013528585A (ja) * 2010-04-29 2013-07-11 ハネウェル・インターナショナル・インコーポレーテッド テトラフルオロプロペンの製造方法
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Publication number Priority date Publication date Assignee Title
WO2020247423A1 (fr) 2019-06-04 2020-12-10 The Chemours Company Fc, Llc Compositions de 2-chloro-3,3,3-trifluoropropène (1233xf) et leurs procédés de fabrication et d'utilisation
WO2021132390A1 (fr) * 2019-12-26 2021-07-01 Ａｇｃ株式会社 Procédé de production de 1-chloro-2,3,3-trifluoropropène
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TWI798875B (zh) * 2020-10-15 2023-04-11 日商昭和電工股份有限公司 蝕刻氣體及其製造方法、以及、蝕刻方法、半導體元件之製造方法
CN115557827A (zh) * 2022-08-29 2023-01-03 西安近代化学研究所 一种3-氯-3,3-二氟丙烯的制备方法

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