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WO2021132390A1 - Procédé de production de 1-chloro-2,3,3-trifluoropropène - Google Patents

Procédé de production de 1-chloro-2,3,3-trifluoropropène Download PDF

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Publication number
WO2021132390A1
WO2021132390A1 PCT/JP2020/048272 JP2020048272W WO2021132390A1 WO 2021132390 A1 WO2021132390 A1 WO 2021132390A1 JP 2020048272 W JP2020048272 W JP 2020048272W WO 2021132390 A1 WO2021132390 A1 WO 2021132390A1
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Prior art keywords
chloro
trifluoropropene
reaction
producing
amount
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Japanese (ja)
Inventor
卓也 岩瀬
厚史 藤森
敦司 藤本
聡史 河口
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2021567575A priority Critical patent/JP7647581B2/ja
Priority to CN202080088905.2A priority patent/CN114845982A/zh
Publication of WO2021132390A1 publication Critical patent/WO2021132390A1/fr
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    • 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
    • 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

Definitions

  • the present invention relates to a method for producing 1-chloro-2,3,3-trifluoropropene.
  • HCFO-1233yd 1,3,3-trifluoropropene
  • 1233yd 3,3-dichloro-1,1,1,2,2-. pentafluoropropane (CF 3 -CF 2 -CHCl 2.
  • HCFC-225ca 1,3-dichloro-1,1,2,2,3-pentafluoropropane
  • ClF 2 -CF 2 -CClFH 1,3-dichloro-1,1,2,2,3-pentafluoropropane
  • GWP small global warming coefficient
  • Patent Document 1 3-chloro-1,1,2,2-tetrafluoropropane (CHF 2 -CF 2- CH 2 Cl. HCFC-244ca; hereinafter, also referred to as 244ca) is used as a method for producing 1233yd.
  • a method of defluoridating hydrogen reaction in the presence of a base has been shown.
  • An object of the present invention is to provide a method for producing 1233 yd, which can reduce the amount of propyne produced and has an excellent conversion rate of 244 ca, which is a raw material.
  • the present inventors desire to carry out a 244ca defluorinated hydrogen reaction in the presence of a phase transfer catalyst, an organic solvent having a relative permittivity of 30 or more, and a base. We have found that the effect of the above can be obtained, and have reached the present invention.
  • [1] It is characterized by hydrogen fluoride reaction of 3-chloro-1,1,2,2-tetrafluoropropane in the presence of a phase transfer catalyst, an organic solvent having a relative permittivity of 30 or more, and a base.
  • a method for producing 1-chloro-2,3,3-trifluoropropene [2] The 1-chloro-2,3,3-trifluoro according to [1], wherein the mass ratio of the amount of the phase transfer catalyst used to the amount of the organic solvent used is 0.020 to 0.20.
  • Propen manufacturing method Propen manufacturing method.
  • the defluorinated hydrogen reaction is further carried out in the presence of water, and at the interface between the aqueous phase containing a base and the organic phase containing 3-chloro-1,1,2,2-tetrafluoropropane.
  • the base is used in the form of a base solution, and the amount of the solvent used in the base solution is relative to the amount of 3-chloro-1,1,2,2-tetrafluoropropane used (100 parts by mass).
  • the amount of the phase transfer catalyst used is 0.1 to 3 parts by mass with respect to the amount of 3-chloro-1,1,2,2-tetrafluoropropane used (100 parts by mass).
  • the amount of the organic solvent used is 1 to 30 parts by mass with respect to the amount of 3-chloro-1,1,2,2-tetrafluoropropane used (100 parts by mass) [1] to [11].
  • the organic solvent was recovered from the reaction solution containing trifluoropropene and the organic solvent, and in the presence of the recovered organic solvent, phase transfer catalyst, and base, 3-chloro-1,1,2,2-tetra.
  • a method for producing 1-chloro-2,3,3-trifluoropropene which comprises reacting fluoropropane with hydrogen fluoride.
  • a reaction solution containing 1-chloro-2,3,3-trifluoropropene was obtained by the production method according to any one of [1] to [13], and 1-chloro-2 was obtained from the reaction solution.
  • a method for producing 1-chloro-2,3,3-trifluoropropene which comprises separating 3,3-trifluoropropene.
  • the method for separating 1-chloro-2,3,3-trifluoropropene from the reaction solution is at least one selected from the group consisting of a separation and purification method, a washing treatment with water, and a solid adsorption treatment. 14].
  • the meanings of the terms in the present invention are as follows.
  • the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the abbreviation of the compound is described in parentheses after the compound name, but in the present specification, the abbreviation is used instead of the compound name as necessary.
  • 1233yd has Z-form and E-form which are geometric isomers depending on the position of the substituent on the double bond.
  • HCFO-1233yd (Z) represents a Z form
  • HCFO-1233yd (E) represents an E form.
  • Amount used means the total amount of A added into the reactor for use in the production of 1233 yd.
  • A is a component used in the reaction, and examples thereof include 244ca, which will be described later, a phase transfer catalyst, an organic solvent having a relative permittivity of 30 or more, a base, and a solvent.
  • the method for producing 1233yd of the present invention is to perform a hydrogen fluoride reaction of 244ca in the presence of a phase transfer catalyst, an organic solvent having a relative permittivity of 30 or more (hereinafter, also referred to as a specific organic solvent), and a base. It is characterized by.
  • the 244ca defluorinated hydrogen reaction in the production method of the present invention is a reaction represented by the following formula 1.
  • the amount of propyne produced can be reduced, and the conversion rate of 244ca, which is a raw material, is excellent.
  • the details of this reason have not been clarified, but it is presumed to be due to the following reasons.
  • propyne eg, 1-chloro-3,3-difluoropropine
  • the present inventors improved the reaction rate of 244ca, shortened the reaction time, and shortened the period during which the produced 1233yd was present in the reaction system.
  • 244ca is a compound known as a raw material or an intermediate for producing a fluorine-containing compound.
  • 244ca is, for example, chlorine-containing 2,2,3,3-tetrafluoropropanol (TFPO) with thionyl chloride (SOCl 2 ) in the presence of N, N-dimethylformamide (DMF), as shown in Formula 2 below. It can be manufactured by the method of converting. This method can be carried out in the liquid phase or the gas phase.
  • a general reactor such as a glass flask, a SUS autoclave, and a glass lining reactor can be used as the reactor.
  • a glass flask it is preferable to install a glass distillation column filled with Raschig rings and simultaneously generate and separate 244 ca.
  • the amount of DMF added to 1 mol of TFPO is preferably 0.001 to 0.2 mol, and the amount of thionyl chloride added is preferably about 0.5 to 1.5 mol.
  • DMF acts catalytically to promote the reaction. Since the reaction of formula 2 proceeds quantitatively in equimolar amounts, it is not necessary that either one is excessive.
  • thionyl chloride at a rate such that the temperature fluctuation due to the reaction progress is within 30 ° C.
  • thionyl chloride reacts with water and is hydrolyzed to SO 2 and HCl.
  • 3-chlorosulfinyloxy-1,1,2,2-tetrafluoropropane is also hydrolyzed to decompose into TFPO, SO 2 and HCl. In order to prevent these, it is preferable to replace the atmosphere in the reactor with dry nitrogen gas.
  • TFPO reacts with thionyl chloride by the addition of thionyl chloride to produce 3-chlorosulfinyloxy-1,1,2,2-tetrafluoropropane.
  • 3-chlorosulfinyloxy-1,1,2,2-tetrafluoropropane is heated, it undergoes a sulfur dioxide desulfurization reaction to produce 244ca.
  • the heating temperature is preferably 70 to 150 ° C, particularly preferably 90 to 130 ° C.
  • the rate of temperature rise is arbitrary, but it is slowed down to about 1 to 2 ° C./min in order to avoid insufficient treatment of the produced sulfur dioxide and insufficient recovery of the produced 244ca. It is desirable to adjust the production rate by raising the temperature at a rate.
  • 3-chlorosulfinyloxy-1,1,2,2-tetrafluoropropane for example, 3-chlorosulfinyloxy-1,1,2,2-tetrafluoro
  • the solvent has a boiling point higher than the reaction temperature of the 3-chlorosulfinyloxy-1,1,2,2-tetrafluoropropane decomposition reaction, and is a solvent that does not easily react with the compounds involved in the reaction represented by the formula 2, and is aprotic.
  • a sex solvent Specific examples include dimethyl sulfoxide, DMF and the like.
  • the amount of the solvent used is preferably 0.5 to 3 mol with respect to 1 mol of 3-chlorosulfinyloxy-1,1,2,2-tetrafluoropropane.
  • the crude product of 244ca produced through the reaction of Equation 2 is usually gaseous.
  • This crude product is treated to remove hydrochloric acid and sulfur dioxide by a method such as washing with water, and dried with a desiccant such as calcium chloride or molecular sieve to remove impurities, and a composition containing 244ca is subjected to a method such as a cold trap. Can be collected at.
  • the obtained composition containing 244ca can be used as it is or by further purifying it, for example, as a composition having a purity of 99.5% by mass or more and used in the production method of the present invention.
  • a composition having a high purity of 244ca that has undergone a purification step may be used, and a composition containing components other than 244ca and 244ca (for example, impurities). You may use the thing.
  • the impurity is an impurity active in the reaction of the present invention, it is preferable to remove it in advance.
  • the product it is preferable to remove TFPO from the inside as much as possible.
  • 244ca obtained by a production method other than the above may be used.
  • 1,1,2,2,3-pentafluoropropane hereinafter, also referred to as 245ca
  • a catalyst containing a compound having at least one selected from Cr and Al. a compound having at least one selected from Cr and Al.
  • a chlorine-containing compound having 1 or 2 carbon atoms preferably carbon tetrachloride, chloroform, dichloromethane, trichlorethylene, or tetrachloroethylene
  • a catalyst preferably a metal catalyst
  • the base is not particularly limited as long as it is a base capable of carrying out a defluorination hydrogen reaction.
  • the base preferably contains at least one base selected from the group consisting of metal hydroxides, metal oxides and metal carbonates in terms of availability, reaction time and reaction yield.
  • the base may be used alone or in combination of two or more.
  • metal hydroxides include alkaline earth metal hydroxides and alkali metal hydroxides.
  • alkaline earth metal hydroxides include magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.
  • alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
  • the metal constituting the metal oxide include alkali metal elements, alkaline earth metal elements, transition metal elements, Group 12 metal elements in the periodic table, and Group 13 metal elements. Among them, alkali metal elements, alkaline earth metal elements, group 6 metal elements, group 8 metal elements, group 10 metal elements, group 12 metal elements, and group 13 metal elements in the periodic table are preferable, and sodium and calcium are preferable. , Chromium, iron, zinc, aluminum are particularly preferred.
  • the metal oxide may be an oxide containing one kind of metal, or may be a composite oxide of two or more kinds of metals. As the metal oxide, sodium oxide, calcium oxide, chromium oxide (chromia), aluminum oxide (alumina), and zinc oxide are preferable, and alumina and chromaa are particularly preferable, from the viewpoint of reaction time and reaction yield.
  • metal carbonates examples include alkaline earth metal carbonates and alkali metal carbonates.
  • alkaline earth metal carbonates include metal carbonates such as beryllium, magnesium, calcium, strontium, barium, and radium.
  • alkali metal carbonates include carbonates of metals such as lithium, sodium, potassium, rubidium, cesium, and francium.
  • a metal hydroxide is preferable from the viewpoint of reaction time and reaction yield, and at least one of potassium hydroxide and sodium hydroxide is particularly preferable.
  • the metal hydroxide may be used alone or in combination of two or more.
  • the base is preferably used in a solution state in which the base is dissolved in a solvent.
  • the solvent is not particularly limited as long as it can dissolve a predetermined amount of base and does not contribute to the hydrogen fluoride reaction.
  • water is preferable from the viewpoint that the alkali metal hydroxide can be sufficiently dissolved and there are no side reactions derived from the solvent.
  • the base is preferably a compound that dissolves 1 g or more in 1 L of water, more preferably a compound that dissolves 100 g or more, and particularly preferably a compound that dissolves 200 g or more.
  • a solution in which a base is dissolved in a solvent is referred to as a "base solution”, and when the solvent is water, it is referred to as a "base aqueous solution”.
  • phase transfer catalyst examples include a quaternary ammonium salt, a quaternary phosphonium salt, a quaternary ammonium salt, a sulfonium salt, a crown ether, and the like. preferable.
  • the phase transfer catalyst may be used alone or in combination of two or more.
  • Examples of the quaternary ammonium salt include compounds represented by the following formula i.
  • R 11 to R 14 independently represent a monovalent hydrocarbon group or a monovalent hydrocarbon group to which a functional group inert to the reaction is bonded, and Y 1 to Y 1 to an anion. Represent.
  • Examples of the hydrocarbon group in R 11 to R 14 include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group, and an alkyl group and an aryl group are preferable.
  • the number of carbon atoms of R 11 to R 14 is preferably 4 to 100.
  • R 11 to R 14 may be the same or different from each other.
  • the functional group is appropriately selected depending on the reaction conditions, but is a halogen atom, an alkoxycarbonyl group, and an acyloxy. Examples thereof include a group, a nitrile group, an acyl group, a carboxy group, an alkoxy group and the like.
  • R 11 R 12 R 13 R 14 N + include tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, methyltri-n-octylammonium, cetyltrimethylammonium, and benzyltrimethyl.
  • Examples thereof include ammonium, benzyltriethylammonium, cetylbenzyldimethylammonium, cetylpyridinium, n-dodecylpyridinium, phenyltrimethylammonium, phenyltriethylammonium, N-benzylpicolinium, pentamethonium and hexamethonium.
  • Examples thereof include ions, benzene sulfonate ions and p-toluene sulfonate ions, and chlorine ions, bromine ions, iodine ions, hydrogen sulfate ions and hydroxide ions are preferable.
  • R 11 R 12 R 13 R 14 N + Tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, methyltri-n-octylammonium.
  • Y 1- Fluoride ion, chloride ion, bromine ion, iodine ion, hydroxide ion.
  • TBAC tetra-n-butylammonium chloride
  • TBAB tetra-n-butylammonium bromide
  • TOMAC methyltri-n-octylammonium chloride
  • Examples of the quaternary phosphonium salt include compounds represented by the following formula ii.
  • R 21 to R 24 independently represent a monovalent hydrocarbon group, and Y 2- represents an anion.
  • Examples of the hydrocarbon group in R 21 to R 24 include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and the like, and an alkyl group and an aryl group are preferable.
  • quaternary phosphonium examples include tetraethylphosphonium, tetra-n-butylphosphonium, ethyltri-n-octylphosphonium, cetiltriethylphosphonium, cetiltri-n-butylphosphonium, Examples thereof include n-butyltriphenylphosphonium, n-amyltriphenylphosphonium, methyltriphenylphosphonium, benzyltriphenylphosphonium and tetraphenylphosphonium.
  • Y 2-in formula ii chlorine ion, fluorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, hydrogen sulfate ion, hydroxide ion, acetate ion , Benzoate ion, benzenesulfonate ion, p-toluenesulfonate ion and the like, and fluorine ion, chlorine ion and bromine ion are preferable.
  • Examples of the quaternary arsonium salt include compounds represented by the following formula iii.
  • R 31 to R 34 each independently represent a monovalent hydrocarbon group, and Y 3- represents an anion.
  • hydrocarbon group in R 31 to R 34 include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group, and examples thereof include an alkyl group and an aryl group.
  • Y 3- in Formula iii preferably a halogen ion, fluorine ion, chlorine ion, bromine ion is particularly preferred.
  • quaternary arsonium salt examples include triphenylmethylarsonium fluoride, tetraphenylarsonium flolide, triphenylmethylarsonium chloride, tetraphenylarsonium chloride, tetraphenylarsonium bromide, and triphenyl. Methylarsonium chloride is preferred.
  • Examples of the sulfonium salt include compounds represented by the following formula iv.
  • R 41 to R 43 each independently represent a monovalent hydrocarbon group, and Y 4- represents an anion.
  • Examples of the hydrocarbon group in R 41 to R 43 include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and the like, and an alkyl group and an aryl group are preferable.
  • Y 4-in Formula iv preferably a halogen ion, fluorine ion, chlorine ion, bromine ion is particularly preferred.
  • the sulfonium salt include di-n-butylmethyl sulfonium iodide, tri-n-butyl sulfonium tetrafluoroborate, dihexyl methyl sulfonium iodide, dicyclohexylmethyl sulfonium iodide, dodecyl methyl ethyl sulfonium chloride, and tris (diethylamino).
  • Sulfonium difluorotrimethyl silicate is mentioned, and dodecylmethylethyl sulfonium chloride is preferable.
  • crown ethers include 18-crown-6, dibenzo-18-crown-6, and dicyclohexyl-18-crown-6.
  • the specific organic solvent is an organic solvent having a relative permittivity of 30 or more.
  • the relative permittivity of the specific organic solvent is 30 or more, and from the viewpoint that the effect of the present invention is more excellent, 37 or more is preferable, 40 or more is particularly preferable, 120 or less is particularly preferable, and 60 or less is particularly preferable.
  • Examples of the specific organic solvent include dimethyl sulfoxide (DMSO) (47.2), acetonitrile (36.6), nitromethane (37.3), nitrobenzene (35.6), methanol (33.0) and the like, and the reaction Dimethyl sulfoxide, acetonitrile and nitromethane are preferable, and dimethyl sulfoxide and acetonitrile are particularly preferable, from the viewpoint of further improving the yield and the reaction rate of 244ca.
  • the specific organic solvent may be used alone or in combination of two or more. The relative permittivity of the specific organic solvent can be confirmed by the Chemical Society of Japan, I-770-777, revised 5th edition, Basic Edition, Chemistry Handbook.
  • 1233yd is produced by the reaction of 244ca with a base and the defluorination hydrogen reaction of 244ca in the presence of a base, a phase transfer catalyst and a specific organic solvent.
  • the production method of the present invention may be carried out by a solid phase reaction or a liquid phase reaction, but it is carried out by a liquid phase reaction because the reaction rate, the yield of 1233 yd and the selectivity are more excellent. It is preferable to do so.
  • a solid-phase reaction a method of bringing a base in a solid state into contact with 244ca in a gaseous state can be mentioned.
  • the liquid phase reaction a method of bringing a base contained in a base solution (preferably a base aqueous solution) into contact with 244ca in a liquid state can be mentioned.
  • the manufacturing method of the present invention may be carried out in a batch type, a semi-continuous type or a continuous distribution type.
  • the reaction time can be appropriately adjusted according to each mode.
  • a base, a phase transfer catalyst, a specific organic solvent and 244ca are introduced into the reactor, and each component is mixed in the reactor.
  • the defluorination hydrogen reaction of 244ca proceeds in the reactor, and a reaction solution containing 1233yd and a specific organic solvent and the like is obtained.
  • water is preferable to use water as the solvent for the defluorinated hydrogen reaction from the viewpoint that the effect of the present invention is more exerted.
  • the solvent can be introduced into the reactor in the state of the above-mentioned base solution (preferably an aqueous base solution).
  • the 244ca defluorinated hydrogen reaction proceeds at the interface between the aqueous phase containing a base and the organic phase containing 244ca. Therefore, it is preferable to mix each component by a stirring means (for example, a static mixer or the like) so that the base and 244ca come into good contact with each other.
  • a stirring means for example, a static mixer or the like
  • 1233 yd contained in the reaction solution derived from the reactor is recovered. Specifically, when an aqueous base solution is used, the reaction solution is allowed to stand after the reaction is completed to separate the reaction solution into an organic phase and an aqueous phase, and then 1233 yd contained in the organic phase is separated and purified by distillation or the like. Collect by method. According to the production method of the present invention, the selectivity of 1-chloro-3,3-difluoropropine can be reduced to 0.2% or less, so that 1233 yd contained in the organic phase can be easily separated and purified.
  • the organic phase contains a specific organic solvent and 1233 yd, and may contain unreacted by-products such as 244ca, 1-chloro-3,3-difluoropropine.
  • 244ca is contained in the product, it is preferable to carry out highly accurate distillation because the boiling points of 244ca and 1233yd (Z) are close to each other.
  • the E-form and Z-form of 1233yd may be separated by a separation and purification method such as distillation.
  • the aqueous phase contains water and may contain a specific organic solvent, a solvent, 1233 yd and the like.
  • a part of the specific organic solvent is decomposed, and the decomposed product may be contained in the organic phase or the aqueous phase.
  • the decomposition product contained in the organic phase can be separated from 1233 yd by a separation and purification method such as distillation, a water washing treatment by washing with water, a solid adsorption treatment in which the organic phase is brought into contact with a solid adsorbent, or a combination thereof.
  • the solid adsorbent include activated carbon, zeolite, silica, alumina and the like. Two or more kinds of solid adsorbents may be used in combination.
  • DMSO DMSO
  • a part of DMSO is decomposed and may be contained in the organic phase or the aqueous phase as dimethyl sulfide.
  • Dimethyl sulfide contained in the organic phase can be separated from 1233 yd by a separation and purification method such as distillation, a water washing treatment by washing with water, a solid adsorption treatment in which the organic phase is brought into contact with a solid adsorbent, or a combination thereof.
  • the solid adsorbent include activated carbon, zeolite, silica, alumina and the like. Two or more kinds of solid adsorbents may be used in combination.
  • Activated carbon is preferably used because it has high adsorptivity to dimethyl sulfide.
  • the content of dimethyl sulfide is preferably 0.1 to 10 mass ppm, more preferably 0.3 to 5 mass ppm, and 0.5 to 3 mass ppm, based on the total amount of the composition containing 1233 yd. Is even more preferable. If it is at least the lower limit value, it is advantageous in terms of manufacturing cost, and the odor peculiar to the solvent can be reduced. If it is not more than the upper limit, the pungent odor caused by dimethyl sulfide can be reduced.
  • the reaction solution is also excellent in two-layer separability. The details of this reason have not been clarified, but it is presumed that it is due to the action of a specific organic solvent. If the reaction solution has excellent bilayer separability, there are advantages such as easy recovery of 1233 yd, easy reuse of each component, and shortening of the process time.
  • the acid content i.e., the content of chloride and fluoride ions, is preferably less than 10 mass ppm, more preferably less than 1 mass ppm, most preferably less than 0.1 mass ppm, relative to the total amount of purified 1233 yd. ..
  • the water concentration in the purified 1233 yd is preferably 2000 mass ppm, more preferably less than 1500 mass ppm, further preferably 1000 mass ppm, and most preferably less than 100 mass ppm.
  • the oxygen concentration in the purified 1233 yd is preferably 1000 mass ppm or less, and particularly preferably 500 mass ppm or less. Outside the above range, decomposition of 1233 yd may occur and degreasing cleaning performance may be impaired.
  • the material of the reactor is not particularly limited as long as it is inactive to the components used in the production method of the present invention and the components contained in the reaction solution obtained after the reaction and is corrosion resistant.
  • Specific examples of the material of the reactor include alloys such as glass, iron, nickel, and stainless steel containing iron as a main component.
  • the reaction temperature in the hydrogen defluorination reaction is preferably 40 to 90 ° C., more preferably 45 ° C. or higher, still more preferably 55 ° C. or higher, from the viewpoints that the effect of the present invention is more excellent and the reaction rate is further improved.
  • 60 ° C. or higher is particularly preferable
  • 80 ° C. or lower is more preferable
  • 75 ° C. or lower is further preferable
  • 70 ° C. or lower is particularly preferable, from the viewpoint that the effect of the present invention is more excellent and the selectivity of 1233 yd is further improved. ..
  • the 1233yd obtained by the production method of the present invention may be in the E form or the Z form, or may be a mixture thereof.
  • the boiling point of 244ca is 53 ° C.
  • the boiling point of 1233yd (Z) is 54 ° C.
  • the boiling point of 1233yd (E) is 47 to 48 ° C.
  • Specific examples of the use of 1233yd obtained by the production method of the present invention include a cleaning agent, a refrigerant, a foaming agent, a solvent, and an aerosol.
  • the specific organic solvent contained in the organic phase of the above-mentioned reaction solution can be recovered and reused as the specific organic solvent used in the production method of the present invention.
  • the reaction solution is excellent in two-layer separability, so that the recovery efficiency of the specific organic solvent is excellent.
  • the specific organic solvent was recovered from the reaction solution containing 1233 yd and the specific organic solvent obtained as described above, and in the presence of the recovered specific organic solvent, phase transfer catalyst, and base, 244ca
  • a method of producing 1233 yd by carrying out a defluorinated hydrogen reaction can be mentioned.
  • Specific examples of the method for recovering the specific organic solvent from the reaction solution include a method for separating and purifying the organic phase contained in the reaction solution (for example, distillation).
  • the amount of the base used is preferably 0.8 to 3.0 mol, more preferably 1.0 to 2.5 mol, and particularly preferably 1.2 to 2.0 mol, based on 1 mol of 244 ca.
  • the concentration of the base in the base solution is preferably 20 to 55% by mass, more preferably 30 to 48% by mass, and 38 to 44% by mass. % Is particularly preferable.
  • the reaction rate can be further improved, and when it is at least the upper limit value, the generation of propyne can be further reduced and the selectivity of 1233 yd can be further improved.
  • the base is used in the form of the above-mentioned base solution (preferably a base aqueous solution)
  • the amount of the solvent (preferably water) used is 98 to 300 parts by mass with respect to the amount of 244 ca used (100 parts by mass). Is preferable, and 103 to 200 parts by mass is particularly preferable.
  • the amount of water used is within the above range, the two-layer separability of the reaction solution is more excellent.
  • the amount of the phase transfer catalyst used is preferably 0.1 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, and 0.5 to 1.5 parts by mass with respect to the amount of 244 ca used (100 parts by mass).
  • the portion is more preferable. If it is equal to or higher than the lower limit, the conversion rate of 244ca and the yield of 1233yd are further improved. If it is less than the upper limit, the two-layer separability is excellent and the cost is also advantageous.
  • the amount of the specific organic solvent used is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and particularly preferably 10 to 20 parts by mass with respect to the amount of 244 ca used (100 parts by mass).
  • the formation of propyne can be further reduced, and the reaction rate and the two-layer separability of the reaction solution are more excellent. If it is not more than the upper limit, the two-layer separability and the volumetric efficiency of the reaction are excellent, which is also advantageous in terms of cost.
  • the mass ratio of the amount of the phase transfer catalyst used to the amount of the specific organic solvent used is preferably 0.020 to 0.20, more preferably 0.020 to 0.090, and 0. .040 to 0.070 is even more preferable. If it is at least the lower limit, the reaction can proceed efficiently. When it is not more than the upper limit value, the two-layer separability of the reaction solution is more excellent, and the formation of propyne can be reduced.
  • the base is used in the form of the above-mentioned base solution (preferably a base aqueous solution)
  • the mass ratio of the amount of the specific organic solvent used to the amount of the solvent preferably water used (amount of the specific organic solvent used / solvent).
  • the amount used is preferably 0.01 to 0.50, more preferably 0.05 to 0.30, and particularly preferably 0.08 to 0.16.
  • the amount used is preferably 0.01 to 0.50, more preferably 0.05 to 0.30, and particularly preferably 0.08 to 0.16.
  • the production of propyne can be further reduced, and the reaction can proceed efficiently.
  • it is not more than the upper limit value the two-layer separability of the reaction solution is more excellent.
  • Examples 1-1 to 1-3 and Examples 2-1 to 2-8 are examples, and Examples 1-4 and 2-9 are comparative examples. However, the present invention is not limited to these examples.
  • the conversion rate indicates the ratio (unit:%) of the molar amount of the raw material (244ca) consumed in the reaction to the molar amount of the raw material (244ca unless otherwise specified) used in the reaction.
  • the selectivity refers to the ratio (unit:%) of the amount (molar amount) of the product (1233yd or 1-chloro-3,3-difluoropropine) produced to the total amount of the product.
  • the yield (%) is a numerical value indicating the molar amount of the product (1233yd) recovered from the organic phase obtained in the reaction as a ratio (unit:%) to the molar amount of 244ca introduced into the reaction system. Is.
  • reaction rate constant The reaction rate constant was calculated by the least squares method so that the difference between the conversion rate experimentally obtained from the concentration of 244 ca at each time and the conversion rate calculated from the following reaction rate equation was minimized.
  • Reaction rate equation: ⁇ d [244ca] / dt k [244ca] [KOH]
  • k the rate constant
  • t the time
  • [244ca] the concentration of 244ca
  • [KOH] is the concentration of KOH.
  • the two-layer separability is determined by visually observing the reaction solution after allowing the reaction solution containing the organic phase and the aqueous phase to stand for 1 hour after the reaction for obtaining 1233 yd is completed, and according to the following criteria. Was evaluated.
  • ⁇ The interface between the organic phase and the aqueous phase is clear.
  • ⁇ A small amount of emulsion or solid suspended matter is observed at the interface between the organic phase and the aqueous phase.
  • X Most or all of the solution is an emulsion
  • 244ca was produced by the following method.
  • the following method is a method of obtaining 244ca by chlorinating TFPO with thionyl chloride as shown in the above formula 2.
  • Example 1-1 In an autoclave having a stirrer, 52.9 g of 244ca obtained as described above, 0.529 g of tetra-n-butylammonium bromide (TBAB) as a phase transfer catalyst, and dimethyl sulfoxide (DMSO) as a specific organic solvent. 7.935 g of the above, 131.3 g of a 30 mass% potassium hydroxide (KOH) aqueous solution was added, and the autoclave was heated to 70 ° C. The reaction temperature was maintained at 70 ° C., stirring was continued for 4 hours (reaction time), and then a reaction solution containing an organic phase and an aqueous phase was obtained. The above-mentioned evaluation of the two-layer separability was carried out using the obtained reaction solution. In addition, the organic phase recovered from the reaction solution was washed with water and then analyzed by gas chromatography to calculate the conversion rate, selectivity and yield.
  • KOH potassium hydroxide
  • Examples 1-2 to 1-4, Examples 2-1 to 2-9 In Examples 1-2 to 1-4 and Examples 2-1 to 2-9 in the same manner as in Example 1-1, except that the amount of each component used and the reaction conditions were changed as shown in Table 1 below. A reaction solution and an organic phase were obtained. Using the obtained reaction solution and the organic phase, the same evaluation as in Example 1-1 was carried out.
  • Table 1 MeCN means acetonitrile and MeNO 2 means nitromethane.
  • the KOH concentration means the concentration of KOH in the KOH aqueous solution.
  • KOH equivalent means the amount (mol) of KOH used per mole of 244 ca.
  • the amounts of water, TBAB and the specific organic solvent used all mean the amount used (parts by mass) with respect to the amount used (100 parts by mass) of 244ca.
  • a / B means the mass ratio of the amount of TBAB used to the amount of the specific organic solvent used
  • B / C means the mass ratio of the amount of the specific organic solvent used to the amount of water used.
  • Example 2-4 To the composition (1233yd: 99.9% by mass, dimethyl sulfide: 14% by mass) produced in Example 2-4, 10% by mass of activated carbon (Carborafine, manufactured by Osaka Gas Chemical Co., Ltd.) was added to the composition. , 25 ° C. for 3 days. Then, the activated carbon was removed by filtration, and the composition was recovered. When the composition recovered by gas chromatography was analyzed, 1233 yd was 99.9 mass%, dimethyl sulfide was 2.6 mass ppm, and the recovery rate of 1233 yd was 90.1%.
  • activated carbon Carborafine, manufactured by Osaka Gas Chemical Co., Ltd.
  • Example 2-2 The composition produced in Example 2-2 (1233yd: 99.9% by mass, dimethyl sulfide: 184% by mass) was distilled, and the distillate was recovered. When the distillate recovered by gas chromatography was analyzed, 1233 yd was 99.9 mass%, dimethyl sulfide was 0.6 mass ppm, and the recovery rate of 1233 yd was 85.3%.

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  • 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 de 1-chloro-2,3,3-trifluoropropène, qui peut réduire la quantité de propyne générée, et qui fournit un excellent taux de conversion du 3-chloro-1,1,2,2-tétrafluoropropane en tant que matière première.　Le procédé de production de 1-chloro-2,3,3-trifluoropropène selon la présente invention implique la déshydrofluoration du 3-chloro-1,1,2,2-tétrafluoropropane en présence d'une catalyse par transfert de phase, d'un solvant organique ayant une constante diélectrique de 30 ou plus, et d'une base.
PCT/JP2020/048272 2019-12-26 2020-12-23 Procédé de production de 1-chloro-2,3,3-trifluoropropène Ceased WO2021132390A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2018092780A1 (fr) * 2016-11-15 2018-05-24 旭硝子株式会社 Procédé de fabrication de １－chloro－２，３，３－trifluoropropène
WO2019203318A1 (fr) * 2018-04-19 2019-10-24 Ａｇｃ株式会社 Procédé de production de fluorooléfine
WO2019203319A1 (fr) * 2018-04-19 2019-10-24 Ａｇｃ株式会社 Procédé de production de fluorooléfine

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9963410B2 (en) * 2015-02-27 2018-05-08 Daikin Industries, Ltd. Method for producing 1-chloro-2,3,3-trifluoropropene
WO2018101323A1 (fr) * 2016-11-30 2018-06-07 旭硝子株式会社 Procédé de fabrication de １－chloro－２，３，３－trifluoropropène

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2018092780A1 (fr) * 2016-11-15 2018-05-24 旭硝子株式会社 Procédé de fabrication de １－chloro－２，３，３－trifluoropropène
WO2019203318A1 (fr) * 2018-04-19 2019-10-24 Ａｇｃ株式会社 Procédé de production de fluorooléfine
WO2019203319A1 (fr) * 2018-04-19 2019-10-24 Ａｇｃ株式会社 Procédé de production de fluorooléfine

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