WO2019026515A1 - Procédé de production de 1,2-dichloro-1,2-difluoroéthane (hcfc-132), procédé de production de 1-chloro-1,2-difluoroéthylène (hcfo-1122a), et procédé de séparation de hcfc-132 - Google Patents

Procédé de production de 1,2-dichloro-1,2-difluoroéthane (hcfc-132), procédé de production de 1-chloro-1,2-difluoroéthylène (hcfo-1122a), et procédé de séparation de hcfc-132 Download PDF

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WO2019026515A1
WO2019026515A1 PCT/JP2018/025356 JP2018025356W WO2019026515A1 WO 2019026515 A1 WO2019026515 A1 WO 2019026515A1 JP 2018025356 W JP2018025356 W JP 2018025356W WO 2019026515 A1 WO2019026515 A1 WO 2019026515A1
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hcfc
hcfo
mol
difluoroethane
dichloro
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PCT/JP2018/025356
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Japanese (ja)
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臼井　隆
大輔 加留部
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ダイキン工業株式会社
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Priority to CN202310432291.0A priority Critical patent/CN116462565A/zh
Priority to CN202210394820.8A priority patent/CN114634398A/zh
Priority to CN201880050223.5A priority patent/CN110997604A/zh
Priority to CN202310432354.2A priority patent/CN116462566A/zh
Publication of WO2019026515A1 publication Critical patent/WO2019026515A1/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
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
    • C07C19/12—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine having two carbon atoms
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • 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 of producing 1,2-dichloro-1,2-difluoroethane (HCFC-132), a method of producing 1-chloro-1,2-difluoroethylene (HCFO-1122a), and a method of separating HCFC-132 About.
  • 1,2-difluoroethylene (HFO-1132) is reacted with chlorine to form 1,2-dichloro-1,2-difluoroethane (HCFC-132), and dehydrochlorination reaction of HCFC-132
  • HCFO-1122a 1,2-dichloro-1,2-difluoroethane
  • Patent Document 1 1-chloro-1,2-difluoroethylene
  • the above production method uses chlorine, which is a halogen that is difficult to handle, when producing HCFC-132, and uses highly toxic carbon tetrachloride as a solvent, and HCFO-1122a can be conveniently and easily There is room for improvement in order to manufacture efficiently.
  • the present invention relates to a process for producing HCFC-132 using a reducing agent, and a process for producing HCFO-1122a using HCFC-132 obtained by the process as a raw material compound, comprising HCFC-132 and HCFO-1122a It aims at providing a manufacturing method with high selectivity. Another object of the present invention is to provide a method for separating HCFC-132.
  • the present invention relates to the following method for producing HCFC-132, method for producing HCFO-1122a, and method for separating HCFC-132.
  • CFClX-CFClX wherein each X is independently Cl, Br, I or H, provided that at least one of X is Cl, Br or I.
  • Production of HCFC-132 characterized in that it comprises the step of reducing the halogenated ethane represented in the presence of a reducing agent to form 1,2-dichloro-1,2-difluoroethane (HCFC-132) Method.
  • Item The method according to Item 1, wherein the reducing agent is formate. 3.
  • a separation method of HCFC-132 wherein a mixture of HCFC-132 and a boiling point of -10 ° C or less is separated under pressure.
  • Item 8 The separation method according to item 7, wherein the pressure to be applied is 0.01 to 2.0 MPa.
  • the mixture having a boiling point of ⁇ 10 ° C. or less contains at least one selected from the group consisting of CO 2 , N 2 , HCFO-1122a and 2-chloro-1,1-difluoroethylene (HCFC-1122) The separation method described in. 10.
  • HCFC-132 1,1,2-trichloro-1,2-difluoroethane (HCFC-122a), 1,2-dichloro-1,1-difluoroethane (HCFC-132b) and 1,1-dichloro-2,2
  • a composition comprising at least one compound selected from the group consisting of difluoroethane (HCFC-132a).
  • a composition comprising HCFO-1122a and at least one compound selected from the group consisting of HCFC-132, HCFC-1122 and 1,2-dichloro-1,2-difluoroethylene (CFC-1112).
  • Item 12 The composition according to item 11, which is a refrigerant composition.
  • the present invention is a method for producing HCFC-132 by hydrogenating a specific halogenated ethane with a reducing agent, and a method for producing HCFO-1122a using HCFC-132 obtained by the production method as a raw material compound.
  • the method of the present invention is easy to handle as compared with the conventional method in that chlorine and highly toxic carbon tetrachloride are not used, and the selectivity of HCFC-132 and HCFO-1122a is high.
  • pressure means gauge pressure (i.e., a pressure expression with atmospheric pressure being zero) unless otherwise specified.
  • a process for producing 1,2-dichloro-1,2-difluoroethane (HCFC-132) is a compound represented by the general formula (1): CFClX A halogenated ethane represented by —CFClX (wherein each X independently represents Cl, Br, I or H, provided that at least one of X is Cl, Br or I) And reducing in the presence of a reducing agent to produce HCFC-132.
  • the reaction to convert the halogenated ethane of general formula (1) to HCFC-132 can be carried out by hydrogenating the halogenated ethane of general formula (1) in the presence of a reducing agent in a suitable solvent.
  • reducing agents include hydrogen, lithium aluminum hydride, formic acid, formate, sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride.
  • formate is preferable from the viewpoint of obtaining HCFC-132 in high yield.
  • formate salt sodium formate, potassium formate and ammonium formate can be used, and sodium formate and ammonium formate are preferable in terms of water solubility and ease of handling.
  • a catalyst such as palladium black, palladium / carbon, platinum oxide, platinum black, Raney nickel can be used from the viewpoint of obtaining HCFC-132 in high yield.
  • the reaction temperature when performing a reduction reaction using a reducing agent is preferably 20 ° C. to 100 ° C., more preferably 20 ° C. to 80 ° C., and 30 ° C. to 70 ° C. More preferable.
  • the reduction reaction is preferably performed at 0.0 to 2.0 MPa, and more preferably 0.0 to 1.5 MPa.
  • the reduction reaction is completed in 1 to 20 hours from the start of the reaction.
  • the amount of the reducing agent is preferably 1 mol equivalent to 10 mol equivalent, more preferably 1.5 mol equivalent to 8 mol equivalent, and still more preferably 1.5 mol equivalent to 5 mol equivalent based on 1 mol of the halogen necessary for the reduction of the general formula (1).
  • the solvent is not limited as long as the reduction reaction is not adversely affected.
  • a solvent at least one solvent selected from the group consisting of water, ethers, amides, nitriles and alcohols, or the solvent can be used after mixing with other solvents.
  • the ethers are not particularly limited, and examples thereof include diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene and the like.
  • the amides are not particularly limited, and examples thereof include N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAC).
  • the nitriles are not particularly restricted but include, for example, acetonitrile, propionitrile and benzonitrile.
  • the alcohols are not particularly limited, and examples thereof include methanol, ethanol, propanol, isopropanol, n-butyl alcohol, t-butyl alcohol and isoamyl alcohol.
  • At least one selected from the group consisting of water, ethers, amides and alcohols is preferable, and from the viewpoint of obtaining HCFC-132 with high selectivity, DMF is more preferable.
  • the amount of the solvent is not particularly limited as long as the effects of the present invention are not significantly impaired, and for example, 1 to 50 parts by mass is preferable, and 2 to 20 parts by mass with respect to 1 part by mass of the halogenated ethane of the general formula (1). Part is more preferable, and 2 to 10 parts by mass is more preferable.
  • halogenated ethane represented by the general formula (1) for example, 1,1,2,2-tetrachloro-1,2-difluoroethane (CFC-112), 1,2-dibromo-1,2-dichloroethane -1,2-difluoroethane, 1,2-dichloro-1,2-difluoro-1,2-diiodoethane, 1-bromo-1,2,2-trichloro-1,2-difluoroethane, 1,1,2-trichloro -1,2-Difluoro-2-iodoethane, 1-bromo-1,2-dichloro-1,2-difluoro-2-iodoethane, 1,1,2-trichloro-1,2-difluoroethane, 1-bromo-1 2,2-dichloro-1,2-difluoroethane, 1.2-dichloro-1,2-difluoro-1-iodoethane and the like.
  • CFC-112 is preferable in the present invention from the viewpoint of obtaining HCFC-132 and HCFO-1122a with high selectivity.
  • the purity of the halogenated ethane represented by the general formula (1) is 60 mol% to 99.99 mol% from the viewpoint of improving the conversion of the halogenated ethane and improving the selectivity of the target product HCFC-132. Is preferable, 80 mol% to 99.99 mol% is more preferable, and 90 mol% to 99.99 mol% is more preferable.
  • a radical generator When the reduction reaction is carried out, a radical generator can be used.
  • the radical generator include organic radical initiators such as azo compounds and organic peroxides, and inorganic radical initiators such as persulfates, cerium salts and hydrogen peroxide.
  • 2,2′-azobis (2-methylpropionamidine) dihydrochloride 2,2′-azobis (isobutyronitrile), 4,4′-azobis (4-cyanovaleric acid), 1 , 1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2-methylpropane), 2,2′-azobis (2-methylpropionitrile), ⁇ , ⁇ ′-azodiisobutylamidine dihydrochloride Etc. are illustrated.
  • organic peroxide methyl ethyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexyl) Peroxy) cyclohexane etc. are illustrated.
  • persulfates examples include ammonium persulfate, sodium persulfate and potassium persulfate.
  • cerium salts include cerium (IV) ammonium nitrate, cerium (IV) sulfate, cerium (IV) ammonium sulfate, cerium (IV) hydroxide, cerium (IV) oxide and the like.
  • radical generators such as ammonium persulfate (APS), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, from the viewpoint of obtaining HCFC-132 in high yield, 2, Azo compounds such as 2'-azobis (isobutyronitrile) are preferred.
  • the compounding amount of the radical generating agent may be a catalytic amount with respect to the halogenated ethane represented by the general formula (1), and from the point of increasing the reaction rate and the point of suppressing the formation of by-products
  • the amount is preferably 0.01 mol to 5 mol, more preferably 0.05 mol to 1 mol, and still more preferably 0.1 mol to 0.5 mol with respect to 1 mol of the halogenated ethane represented by (1).
  • composition of the present invention comprises HCFC-132 obtained by the production method of the present invention, 1,1,2-trichloro-1,2-difluoroethane (HCFC-122a), 1,2-dichloro-1,1- And at least one compound selected from the group consisting of difluoroethane (HCFC-132b) and 1,1-dichloro-2,2-difluoroethane (HCFC-132a).
  • the process for producing 1-chloro-1,2-difluoroethylene (HCFO-1122a) of the present invention comprises (i) a compound represented by the general formula (1): Halogenated ethane represented by CFClX-CFClX (wherein X is each independently Cl, Br, I or H, provided that at least one of X is Cl, Br or I) Is reduced in the presence of a reducing agent to form a mixture comprising HCFC-132, and (Ii) A step of dehydrochlorinating the HCFC-132 in the mixture produced in the step (i) in the presence of a base to produce HCFO-1122a.
  • the production method of the present invention further includes a step of separating HCFC-132 from the mixture produced in the step (i) between the step (i) and the step (ii), and the HCFC-132 is It is preferable to use for the said process (ii).
  • the method for separating HCFC-132 from the mixture produced in step (i) of the manufacturing method of the present invention is not particularly limited, but it is preferable to separate HCFC-132 under pressure in a reactor.
  • the pressure applied is preferably 0.01 to 2.0 MPa, more preferably 0.1 to 1.5 MPa, and still more preferably 0.5 to 1.0 MPa, from the viewpoint of recovery rate and purity of HCFC-132.
  • the mixture containing HCFC-132 obtained in step (i) of the production method of the present invention includes, in addition to HCFC-132, 1,1,2-trichloro-1,2-difluoroethane (HCFC-122a), 1,2-, Dichloro-1,1-difluoroethane (HCFC-132b), 1,1-dichloro-2,2-difluoroethane (HCFC-132a), carbon dioxide, nitrogen and the like are included.
  • the purity of HCFC-132 before separation in the mixture is preferably 60 mol% to 99.99 mol%, more preferably 80 mol% to 99.99 mol%, and still more preferably 90 mol% to 99.99 mol%.
  • the mixture containing HCFC-132 obtained in step (i) of the production method of the present invention preferably contains a compound having a boiling point of ⁇ 10 ° C. or less, in view of the recovery rate and purity of HCFC-132, and the boiling point is ⁇ 30 ° C. It is more preferable to include the following compounds, and it is further preferable to include a compound having a boiling point of ⁇ 50 ° C. or less.
  • HCFO-122a can be produced by dehydrochlorination reaction of HCFC-132 in the mixture produced in the step (i) in the presence of a base.
  • HCFO-122a can be produced by bringing HCFC-132 in the mixture produced in the step (i) into contact with a basic aqueous solution to cause a dehydrochlorination reaction.
  • the basic aqueous solution is not particularly limited as long as it is an aqueous solution of a basic compound that can carry out the above dehydrochlorination reaction.
  • inorganic basic compounds such as alkali metal hydroxides such as lithium hydroxide aqueous solution, potassium hydroxide aqueous solution and sodium hydroxide aqueous solution, alkaline earth metal hydroxides such as calcium hydroxide, amines, etc.
  • alkali metal alkoxides and the like such as sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and sodium hydroxide aqueous solution.
  • aqueous solution of potassium hydroxide sodium hydroxide, calcium hydroxide or the like from the viewpoint of improving the reaction activity and selectivity of HCFO-1122a, and use an aqueous solution of potassium hydroxide Is more preferred.
  • the concentration of the basic aqueous solution used for the dehydrochlorination reaction is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 20 to 30% by mass from the viewpoint of promoting the dehydrochlorination reaction.
  • the amount of the basic aqueous solution used for the above dehydrochlorination reaction is preferably adjusted to be an alkali amount of 1 to 10 mol equivalent with respect to the amount of separated HCFC-132, and is preferably 1.5 to 5 mol equivalent of alkali The amount is more preferable, and the amount of alkali of 2 to 5 mol equivalent is more preferable.
  • dehydrochlorination of the separated HCFC-132 dehydrochlorination can be carried out by contacting the HCFC-132 with a basic aqueous solution in the presence of a phase transfer catalyst.
  • the phase transfer catalyst is not particularly limited, and quaternary ammonium salts such as tetrabutylammonium bromide (TBAB), trimethylbenzylammonium bromide, triethylbenzylammonium bromide, trioctylmethylammonium chloride (TOMAC), etc .; tetrabutylphosphonium chloride ( In addition to phosphonium salts such as TBPC) and crown ethers such as 15-crown 5, 18-crown 6, known substances such as alkyl ammonium salts, carboxylates and alkyl sulfonates can be used. Among them, quaternary ammonium salts are preferable, and for example, tetrabutylammonium bromide, trioctylmethylammonium bromide, Aliquat 336 and the like can be suitably used.
  • TBAB tetrabutylammonium bromide
  • TOMAC trioctylmethylammoni
  • Aliquat 336 is preferable from the viewpoint of economy and safety.
  • the amount of the phase transfer catalyst is preferably 0.1 to 40 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the separated HCFC-132.
  • the dehydrochlorination reaction is carried out by introducing the separated HCFC-132 and the basic aqueous solution into a reactor, and performing stirring or the like so as to sufficiently contact them.
  • the reaction temperature in the above dehydrochlorination reaction is not particularly limited, but it is preferably 0 to 100 ° C., more preferably 40 to 80 ° C., from the viewpoint of improving the reaction activity and the selectivity of HCFO-1122a.
  • the dehydrochlorination reaction is preferably carried out under pressure.
  • the pressure to be applied is preferably 0.01 to 2.0 MPa, more preferably 0.1 to 1.5 MPa, and still more preferably 0.2 to 1.0 MPa, from the viewpoint of improving the reaction activity and the selectivity of HCFO-1122a.
  • the above dehydrochlorination reaction is completed in 1 to 50 hours from the start of the reaction.
  • the product HCFO-1122a is produced as the dehydrochlorination reaction proceeds.
  • the generated HCFO-1122a can be analyzed by an existing method such as gas chromatography (GC), NMR or the like, and then it is cooled and concentrated and then collected in a container.
  • the composition of the present invention comprises HCFO-1122a obtained by the production method of the present invention, HCFC-132, 2-chloro-1,1-difluoroethylene (HCFC-1122) and 1,2-dichloro-1,2 And at least one compound selected from the group consisting of difluoroethylene (CFC-1112). Moreover, it is preferable that the said composition is a refrigerant
  • the separation method of HCFC-132 of the present invention is a method of separating a mixture of HCFC-132 and boiling point -10 ° C or less under pressure. It is preferred to separate HCFC-132 under pressure in the reactor.
  • the pressure applied is preferably 0.01 to 2.0 MPa, more preferably 0.1 to 1.5 MPa, and still more preferably 0.5 to 1.0 MPa, from the viewpoint of recovery rate and purity of HCFC-132.
  • the purity of HCFC-132 before separation in the mixture is preferably 60 mol% to 99.99 mol%, more preferably 80 mol% to 99.99 mol%, and still more preferably 90 mol% to 99.99 mol%.
  • the mixture having a boiling point of ⁇ 10 ° C. or less preferably contains at least one selected from the group consisting of CO 2 , N 2 , HCFO-1122a and 2-chloro-1,1-difluoroethylene (HCFC-1122).
  • HCFC-132 1,2-Dichloro-1,2-difluoroethane (Example 1)
  • 0.05 mol of CFC-112 0.15 mol of sodium formate, 0.015 mol of ammonium persulfate (APS) and 50 ml of DMF are added, and the temperature is raised to 40 ° C. under atmospheric pressure and then stirring is started to react
  • analysis was appropriately performed by gas chromatography to confirm that CFC-112 and HCFC-122a were consumed, and then allowed to cool. After that, water was added and stirred to obtain HCFC-132 of the liberated organic phase.
  • Example 2 In a 3 L flask, 6 mol of CFC-112 2.0 mol ammonium formate and 800 ml of DMF were added, and the temperature was raised to 40 ° C. under atmospheric pressure conditions and then the stirring was started. 0.1 mol of APS was added to a charge of 0.6 mol and allowed to react. After the start of the reaction, HCFC-132 was obtained in the same manner as Example 1.
  • Example 3 In a 3 L autoclave, 2.5 mol of CFC-112, 9.6 mol of ammonium formate, 0.75 mol of APS and 500 ml of DMF were added, and the temperature was raised to 40 ° C. and then the stirring was started. 0.1 mol of APS was added to a charge of 1.1 mol. Thereafter, the back pressure valve was set to 1.0 MPa, and the reaction was performed under pressure. The recovery operation after the reaction was adjusted so that the pressure when extracting the gas phase was 0.01 to 1.0 MPa. After that, HCFC-132 was obtained in the same manner as Example 1.
  • Table 1 shows the results of Examples 1 to 3.
  • Example 1 the reaction was carried out using sodium formate as the formate, and the time course of the reaction was analyzed by GC and followed. As a result, it was found that HCFC-122a was first generated, then CFC-112 was generated, and finally HCFC-132 as an object was generated.
  • Example 2 when the reaction was carried out using ammonium formate as a formate salt, the target HCFC-132 was obtained with 92 mol% selectivity. The time course of the reaction was analyzed by GC, and it was found that HCFC-122a was formed first, then CFC-112 was formed, and finally HCFC-132 as an object was formed. After completion of the reaction, the organic phase was recovered and its weight was measured to obtain 100 g (yield 37 mol%) of the obtained amount.
  • Example 3 when ammonium formate was used as the formate and the reaction was performed under pressure in an autoclave, the target HCFC-132 was obtained with a selectivity of 81 mol%. After completion of the reaction, the liquid phase was cooled with ice water and depressurized, and after separation, the weight of the organic phase was measured, and the obtained amount was 202 g (yield: 60 mol%), and separated under pressure conditions to recover HCFC-132. The amount could be increased.
  • HCFO-1122a 1-Chloro-1,2-difluoroethylene (HCFO-1122a) (Example 4) 0.38 mol of HCFC-132 obtained in Example 3 and 1.7 g of a quaternary ammonium salt (Aliquat 336) which is a phase transfer catalyst were added to a 500 ml autoclave, cooled to 0 ° C., and then 20% KOH aqueous solution (KOH 0.56 mol) was dropped. After completion of the dropwise addition, the mixture was heated to 35 to 40 ° C. and stirring was continued. The reaction was terminated when the organic phase in the flask disappeared, and the amount of recovered HCFO-1122a was 33 g.
  • Aliquat 336 a quaternary ammonium salt
  • Example 5 After adding 0.6 mol of HCFC-132 obtained in Example 3 and 10 g of Aliquat 336 to a 500 ml autoclave and cooling to 0 ° C., a 32% KOH aqueous solution (1.2 mol of KOH) was dropped. After completion of the dropwise addition, the mixture was heated to 35 to 40 ° C. and stirring was continued. The reaction was terminated when the organic phase in the flask disappeared, and the recovery of HCFO-1122a was measured to be 56 g.
  • Table 2 shows the results of Examples 4 and 5.
  • Example 4 The fraction obtained from Example 4 was analyzed by a gas chromatograph (GC), and the gas phase composition was calculated from the area ratio of GC. The results are shown in Table 3.
  • GC gas chromatograph
  • Example 5 The fraction obtained from Example 5 was analyzed by a gas chromatograph (GC), and the gas phase composition was calculated from the area ratio of GC. The results are shown in Table 4.
  • GC gas chromatograph
  • Example 3 The reaction was carried out by adding 1.2 eq. Of KOH to 132 in Example 4. As a result, a target product 1122a was obtained with a yield of 90 mol% and a purity of 95 mol%. From the gas phase composition shown in Table 3, it can be confirmed that 1122 and 1112 are produced in addition to 1122a.
  • 1122 is a compound obtained by dehydrochlorination reaction of 132a which is a by-product of the reaction in Example 3
  • 1112 is a compound thought to be a compound obtained by dehydrochlorination reaction of 112 in Example 3 Be
  • Example 5 2.0 eq. Of KOH was added to 132 for the reaction to carry out a reaction, whereby a target product 1122a was obtained with a yield of 95 mol% and a purity of 99 mol%.
  • reaction temperature was able to be shortened by raising temperature, and having added the addition amount of KOH aqueous solution, and the addition amount of Aliquat336.
  • concentration of 132a was very low, so it was traced.
  • Comparative Example 1 the target product 1122a was obtained with a yield of 4 mol% and a purity of 20 mol%.
  • the gas phase composition shown in Table 5 resulted in very low concentration of 1122a as compared with Examples 4 and 5.

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production qui présente une sélectivité élevée vis-à-vis du HCFC-132 et dans lequel la manipulation est plus facile que dans les procédés classiques étant donné que ni le chlore ni le tétrachlorure de carbone hautement toxique n'est utilisé. La présente invention concerne particulièrement un procédé de production de HCFC-132 caractérisé en ce qu'il comprend une étape dans laquelle un éthane halogéné représenté par la formule générale CFClX-CFClX (1) (dans laquelle les fractions X sont chacune indépendamment Cl, Br, I, ou H et au moins l'une ou l'autre des fractions X est Cl, Br ou I) est réduit en présence d'un agent réducteur pour produire du 1,2-dichloro-1,2-difluoroéthane (HCFC-132).
PCT/JP2018/025356 2017-07-31 2018-07-04 Procédé de production de 1,2-dichloro-1,2-difluoroéthane (hcfc-132), procédé de production de 1-chloro-1,2-difluoroéthylène (hcfo-1122a), et procédé de séparation de hcfc-132 WO2019026515A1 (fr)

Priority Applications (4)

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CN202310432291.0A CN116462565A (zh) 2017-07-31 2018-07-04 HCFC－132的制造方法以及分离方法和HCFO－1122a的制造方法
CN202210394820.8A CN114634398A (zh) 2017-07-31 2018-07-04 1,2－二氯－1,2－二氟乙烷（hcfc－132）的分离方法
CN201880050223.5A CN110997604A (zh) 2017-07-31 2018-07-04 1,2－二氯－1,2－二氟乙烷(HCFC－132)的制造方法、1－氯－1,2－二氟乙烯(HCFO－1122a)的制造方法和HCFC－132的分离方法
CN202310432354.2A CN116462566A (zh) 2017-07-31 2018-07-04 HCFC－132的制造方法以及分离方法和HCFO－1122a的制造方法

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JP2017148433A JP6610625B2 (ja) 2017-07-31 2017-07-31 １，２−ジクロロ−１，２−ジフルオロエタン（ＨＣＦＣ−１３２）の製造方法、１−クロロ−１，２−ジフルオロエチレン（ＨＣＦＯ−１１２２ａ）の製造方法、及びＨＣＦＣ−１３２の分離方法

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JP6610625B2 (ja) 2019-11-27
CN110997604A (zh) 2020-04-10

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