WO2019203318A1 - Method for producing fluoroolefin - Google Patents

Abstract

Provided is a method for producing, in a liquid phase, a fluoroolefin from hydrofluorocarbon (HFC) or hydrochlorofluorocarbon (HCFC) with high efficiency. A method for producing a fluoroolefin, the method comprising bringing HFC or HCFC, each of which has 3 to 7 carbon atoms and also has, in the molecule thereof, such a structure that a hydrogen atom and a fluorine or chlorine atom are respectively bonded to adjacent two carbon atoms, in a liquid phase into contact with an aqueous alkaline solution in the presence of a phase transfer catalyst and a water-soluble organic solvent capable of dissolving HFC or HCFC to cause the removal of hydrogen chloride or hydrogen fluoride from the HFC or the HCFC, thereby producing a hydrofluoroolefin, a perfluoroolefin, a hydrochlorofluoroolefin or a chlorofluoroolefin.

Description

Method for producing fluoroolefin

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.

In recent years, hydrofluorocarbons and hydrochlorofluorocarbons have been used for cleaning agents, refrigerants, foaming agents, solvents, aerosols and the like. However, it has been pointed out that these compounds may cause global warming. Therefore, halogenated olefins are attracting attention as compounds having a small global warming potential.

As one method for producing halogenated olefins, 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. Alternatively, a reaction for dehydrofluorination is known.

For example, 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. In 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.

In any of these Patent Documents 1 to 3, an example is described in which the dehydrochlorination or dehydrofluorination reaction of hydrofluorocarbon or hydrochlorofluorocarbon is performed using an aqueous alkali solution in a liquid phase reaction. In these reactions, the reaction time is long. Therefore, although improvements such as the use of a phase transfer catalyst have been made, a method capable of producing more efficiently has been demanded.

Japanese Patent No. 3778298 International Publication No. 2017/018412 International Publication No. 2010/074254

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.

The present invention achieves the above object and has the following aspects.
[1] Hydrofluorocarbon (HFC) or 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)). The HFC or HCFC is dehydrochlorinated or dehydrofluorinated to at least one selected from hydrofluoroolefin (HFO), perfluoroolefin (PFO), hydrochlorofluoroolefin (HCFO) and chlorofluoroolefin (CFO) To obtain a fluoroolefin of It is a manufacturing method.

[2] The interaction distance (Ra) between the water-soluble organic solvent and the hydrofluorocarbon or hydrochlorofluorocarbon represented by the following formula (I) based on the Hansen solubility parameter is 25.0 or less. [1] The manufacturing method as described in.
_{Ra = [4 × (δD 1} -δD 2) 2 + (δP 1 -δP 2) 2 + (δH 1 -δH 2) 2] 0.5 (I)
In the formula _{(I), δD 1, δP} 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 .

[3] The production method according to [1] or [2], wherein the water-soluble organic solvent is present in a ratio of 1 to 100 parts by mass with respect to 100 parts by mass of the hydrofluorocarbon or hydrochlorofluorocarbon.
[4] The production method according to any one of [1] to [3], wherein the water-soluble organic solvent is at least one selected from methanol, acetone, tetraethylene glycol dimethyl ether, and tetrahydrofuran.
[5] Any of [1] to [4], wherein the aqueous alkaline solution is an aqueous solution in which at least one base selected from the group consisting of metal hydroxides, metal oxides and metal carbonates is dissolved in water. The manufacturing method of crab.
[6] The production method according to [5], wherein the ratio of the mass of the base to the total mass of the alkaline aqueous solution in the alkaline aqueous solution is 0.5 to 48 mass%.
[7] The production according to any one of [1] to [6], wherein the phase transfer catalyst is present in a ratio of 0.001 to 10 parts by mass with respect to 100 parts by mass of the hydrofluorocarbon or hydrochlorofluorocarbon. Method.
[8] The production method according to any one of [1] to [7], wherein the phase transfer catalyst is a quaternary ammonium salt.
[9] The production according to any one of [1] to [8], wherein the 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.

[11] 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.
[12] The production method according to any one of [1] to [11], wherein the hydrofluorocarbon or hydrochlorofluorocarbon is dichlorotetrafluoropropane, and the fluoroolefin is monochlorotetrafluoropropene.
[13] The dichlorotetrafluoropropane is 2,3-dichloro-1,1,1,2-tetrafluoropropane and / or 3,3-dichloro-1,1,1,2-tetrafluoropropane, The production method according to [12], wherein the monochlorotetrafluoropropene is 1-chloro-2,3,3,3-tetrafluoropropene.

According to the present invention, a fluoroolefin, specifically, a hydrofluoroolefin, a perfluoroolefin, a hydrochlorofluoroolefin, or a chlorofluoroolefin can be efficiently produced in a liquid phase from hydrofluorocarbon or hydrochlorofluorocarbon.
In addition, since the production method of the present invention is carried out by a liquid phase reaction, a reactor smaller than a gas phase reaction can be employed, which is industrially advantageous.

The meaning of terms in this specification and the way of description are as follows.
As for “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. In addition, as abbreviations, only numbers after the hyphen (-) and lower-case alphabetic characters (for example, "1224yd" in "HCFO-1224yd") may be used. Furthermore, (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). In the names and abbreviations of the compounds, when the E-form and Z-form are not specified, 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). The same applies to reactions represented by other formulas. The compound represented by formula (A) is referred to as 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.

The “Hansen solubility parameter of a compound (hereinafter also referred to as“ HSP ”)” 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. The 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)
The reaction to which the production method of the present invention is applied is specifically a reaction shown in the following reaction formula (1). In the formula (1), the above-mentioned HFC or HCFC which is a starting material (raw material) is represented by the formula (A), and the target product which is HFO, PFO, HCFO or CFO is represented by the formula (B). Formula (C) is hydrogen chloride or hydrogen fluoride.

However, the symbols in formula (1) are as follows.
One of X ¹ and X ² is 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.

Conventionally, 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). Are known. 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. In order to efficiently perform the two-phase contact, the stirring conditions and the device are devised, and the phase transfer catalyst is used to promote the reaction. However, increasing the reaction speed and improving the productivity It was not easy.

In the reaction (1), 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). Has found that 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.

Specific examples of reactions to which the production method of the present invention can be applied will be described below. As an example in the case of 3 carbon atoms, a production example of fluoropropene shown in the reactions of the following formulas (1-1) to (12-2), (15-1) and (15-2) Is mentioned. As an example in the case of 4 carbon atoms, there can be mentioned a production example of fluorobutene shown in the following reactions of the formulas (13-1) and (13-2). As an example in the case of 5 carbon atoms, there can be mentioned a production example of fluoropentene shown in the following reactions of the formulas (14-1) and (14-2).

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 A reaction formula for obtaining 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya) from pentafluoropropane (HCFC-225ea) by deHF. 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 A reaction formula for obtaining PFO-1216 from hexafluoropropane (HCFC-226ea) by deHCl.

Formula (3-1) represents 3-chloro-1,1,1,2,2-pentafluoropropane (HCFC-235cb) and / or 3-chloro-1,1,1,2,3-pentafluoropropane By 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). ) To give 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) by deHF. 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). HCHC-1233yd (Z) and / or HCFO-1233yd (E) by dehydrochlorination from HCl.

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). ) To (Z) -1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)) and / or (E) -1-chloro-3,3,3-trifluoropropene This is a reaction formula to obtain (HCFO-1233zd (E)). 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). HCHC-1233zd (Z) and / or HCFO-1233zd (E) by dehydrochlorination from HCl.

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). (Z) -1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)) and / or (E) -1,3,3,3-tetrafluoropropene (HFO-1234ze (E)) 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). ) To obtain HFO-1234ze (Z) and / or HFO-1234ze (E) by deHCl.

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). ) To (Z) -1,2,3,3,3-pentafluoropropene (HFO-1225ye (Z)) and / or (E) -1,2,3,3,3-pentafluoropropene This is a reaction formula to obtain (HFO-1225ye (E)). 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 1,1,1,2,4,4,4-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.

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. A reaction formula for obtaining CFO-1215yb (Z) and / or CFO-1215yb (E) from pentafluoropropane (HCFC-225eb) by deHCl.

In each of the above reactions, 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.

Examples of the reaction for obtaining monochlorotetrafluoropropene from dichlorotetrafluoropropane by deHCl to obtain 1224yd (Z) and / or 1224yd (E) from 234bb and / or 234ea of formula (3-2) by deHCl. It is done.

In the above reaction, 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.

In the reaction (1) according to the production method of the present invention, 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).

In the present invention, 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. For example, 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. In addition, 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.

In the production method of the present invention, 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. Specifically, 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). For example, 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.

When the base is a metal hydroxide, 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.

When the base is a metal oxide, 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. 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, 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. As 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.

When the base is a metal carbonate, examples include alkaline earth metal carbonates and alkali metal carbonates. Examples of the alkaline earth metal carbonate include carbonates of metals such as beryllium, magnesium, calcium, strontium, barium, and radium. Examples of the 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). For example, in the reaction of obtaining 1234yf from 244bb and / or 244eb by deHCl, 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.

Further, for example, in the reaction for obtaining 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) From the viewpoint of improving the selectivity, 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.

In the production method of the present invention, 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.

Examples of the phase transfer catalyst 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.

Specifically, tetra-n-butylammonium chloride (TBAC), tetra-n-butylammonium bromide (TBAB), methyltri-n-octylammonium chloride (TOMAC) and the like are preferable as the quaternary ammonium salt. Of these, tetra-n-butylammonium chloride (TBAC) or tetra-n-butylammonium bromide (TBAB) is preferable from the viewpoint of further promoting the reaction, and tetra-n-butylammonium bromide (TBAB) (from the point of availability). TBAB) is more preferable, and tetra-n-butylammonium chloride (TBAC) is more preferable from the viewpoint of reactivity.

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). In this specification, 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. Have.

As the 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). .

Examples of the water-soluble alcohol include methanol, ethanol, propan-1-ol, butan-1-ol, propan-2-ol, butan-2-ol, 2-methylpropan-2-ol, and 2-methylbutane- Examples of 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. Examples of water-soluble ethers 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. Examples of water-soluble esters 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). ) And the compound (A) are preferably 25.0 or less, more preferably 23.0 or less, and particularly preferably 22.0 or less.
_{Ra = [4 × (δD 1} -δD 2) 2 + (δP 1 -δP 2) 2 + (δH 1 -δH 2) 2] 0.5 (I)

Each formula _{(I), δD 1, δP} 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 .
In the present invention, the interaction distance (Ra) is preferably small, and the lower limit is not particularly limited.

Specifically, for example, when 244bb, 244eb, 234bb, 234ea is used as the compound (A), the interaction distance (Ra) of each compound that is preferable as the water-soluble organic solvent (S) with respect to these compounds (A) ) Is shown in Table 1.

As shown in Table 1, methanol, acetone, tetraglyme, and tetrahydrofuran have an interaction distance (Ra) of 25.0 or less for all of 244bb, 244eb, 234bb, and 234ea. In these dehalogenation reactions, It can be preferably used as the water-soluble organic solvent (S).
Similarly, 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.

The 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. .

For example, in the reaction of obtaining 1234yf from 244bb and / or 244eb by deHCl, the reaction temperature, that is, the temperature in the reactor is preferably 40 to 120 ° C, more preferably 50 to 110 ° C. By setting the reaction temperature within the above range, the reaction rate and the reaction rate are improved, and by-products are easily suppressed. In 244bb, the reaction temperature is preferably 60 to 120 ° C, more preferably 80 to 110 ° C. In 244eb, the reaction temperature is preferably 40 to 80 ° C., more preferably 50 to 70 ° C.

In the reaction of obtaining 1234yf from 244bb and / or 244eb by deHCl, 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.

Further, for example, in the reaction for obtaining 1224yd (Z) and / or 1224yd (E) from 234bb and / or 234ea by deHCl, 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.

In the production method of the present invention, from the viewpoint of industrially producing a large amount of the desired fluoroolefin, 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. Examples of 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. Not. For example, 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. In the production method of the present invention, after completion of the reaction, 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). When recovering the compound (B) from the organic phase containing these, it is preferable to employ a separation and purification method such as general distillation.
In addition, when the unreacted compound (A) remains in the reaction solution, the compound (A) can be concentrated by distillation and recycled as the raw material of the present invention.

On the other hand, 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.
Further, 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.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. Examples 1 to 4 are examples, and examples 5 and 6 are comparative examples.

[Conditions for gas chromatography]
In the production of the following various compounds, the composition analysis of the obtained reaction composition was performed using gas chromatography (GC). DB-1301 (trade name, manufactured by Agilent Technologies, length 60 m × inner diameter 250 μm × thickness 1 μm) was used as the column.

[Example of production of 244bb]
254eb was chlorinated to produce 244bb and 244eb as follows. First, a stainless steel autoclave (internal volume: 6.9 liters) fitted with a quartz tube and a jacket for transmitting light from the light source was cooled to 20 ° C. In this autoclave (hereinafter referred to as a reactor), 2336 g of carbon tetrachloride (CCl ₄ ) and 103 g of 254eb were placed, and then an LED lamp (LHT42N-GE39 manufactured by Mitsubishi Electric Corporation, rated power consumption 42.4 W). Chlorine gas was introduced into the reactor at a flow rate of 3.2 g / min. As the reaction progressed, heat of reaction was generated and the temperature in the reactor rose to 23.8 ° C. The flow rate chlorine gas was introduced for 2 minutes, that is, 0.10 mol of chlorine was introduced per 1 mol of 254eb, and light irradiation was continued until the temperature in the reactor became constant at 20 ° C. The pressure in the reactor was 0.045 MPa before chlorine supply, and the pressure after chlorine supply, that is, the reaction pressure was 0.045 MPa.

After completion of the reaction, the obtained 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.

[Example 1]
A 0.1 L reactor (autoclave) equipped with a thermocouple and a stirring blade was placed in a thermostat and kept at 80 ° C. In this reactor, 61.1 g of a 30% by mass KOH aqueous solution and 24.6 g of 244bb obtained above (KOH: 244bb molar ratio is KOH: 244bb = 2: 1) as a phase transfer catalyst. Tetra-n-butylammonium bromide (TBAB) of 0.25
g, 2.46 g of methanol as the water-soluble organic solvent (S) was added, the reactor was closed, and a pressure test was performed.

After stirring for 2 hours by rotating the stirring blade at 600 rpm, the reactor was taken out from the thermostat and cooled to 0 ° C. with ice water to stop the reaction, and the reaction composition was recovered. As a result of GC analysis of the recovered reaction composition, the conversion rate of 244bb was 33.2%, the yield of 1234yf was 33.2%, and the selectivity was 100%. The results are shown in Table 2.

[Examples 2 to 4]
In Example 1, 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.

The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-080599 filed on April 19, 2018 are cited herein as disclosure of the specification of the present invention. Incorporate.

Claims (13)

1. A hydrofluorocarbon or hydrochlorofluorocarbon having a structure in which the number of carbon atoms is 3 to 7 and a hydrogen atom and a fluorine atom or a chlorine atom are bonded to two adjacent carbon atoms in the molecule, in the liquid phase, In the presence of a phase transfer catalyst and a water-soluble organic solvent capable of dissolving the hydrofluorocarbon or hydrochlorofluorocarbon, contacting with an alkaline aqueous solution, dehydrochlorinating or dehydrofluorinating the hydrofluorocarbon or hydrochlorofluorocarbon, A method for producing a fluoroolefin, which obtains at least one fluoroolefin selected from hydrofluoroolefin, perfluoroolefin, hydrochlorofluoroolefin, and chlorofluoroolefin.
2. The production method according to claim 1, wherein an interaction distance (Ra) between the water-soluble organic solvent represented by the following formula (I) and the hydrofluorocarbon or hydrochlorofluorocarbon is 25.0 or less.
   _{Ra = [4 × (δD 1} -δD 2) 2 + (δP 1 -δP 2) 2 + (δH 1 -δH 2) 2] 0.5 (I)
   In the formula _{(I), δD 1, δP} 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 .
3. 3. The production method according to claim 1, wherein the water-soluble organic solvent is present in a ratio of 1 to 100 parts by mass with respect to 100 parts by mass of the hydrofluorocarbon or hydrochlorofluorocarbon.
4. The production method according to any one of claims 1 to 3, wherein the water-soluble organic solvent is at least one selected from methanol, acetone, tetraethylene glycol dimethyl ether and tetrahydrofuran.
5. The alkaline aqueous solution is an aqueous solution in which at least one base selected from the group consisting of metal hydroxides, metal oxides, and metal carbonates is dissolved in water. Manufacturing method.
6. The production method according to claim 5, wherein a ratio of the mass of the base to the total mass of the alkaline aqueous solution in the alkaline aqueous solution is 0.5 to 48 mass%.
7. The production method according to any one of claims 1 to 6, wherein the phase transfer catalyst is present in a ratio of 0.001 to 10 parts by mass with respect to 100 parts by mass of the hydrofluorocarbon or hydrochlorofluorocarbon.
8. The production method according to any one of claims 1 to 7, wherein the phase transfer catalyst is a quaternary ammonium salt.
9. The production method according to any one of claims 1 to 8, wherein the phase transfer catalyst is tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, or methyltri-n-octylammonium chloride.
10. The production method according to any one of claims 1 to 9, wherein the hydrofluorocarbon or hydrochlorofluorocarbon is monochlorotetrafluoropropane, and the fluoroolefin is tetrafluoropropene.
11. The monochlorotetrafluoropropane is 2-chloro-1,1,1,2-tetrafluoropropane and / or 3-chloro-1,1,1,2-tetrafluoropropane, and the tetrafluoropropene is 2,3 The production method according to claim 10, which is 1,3,3-tetrafluoropropene.
12. The production method according to any one of claims 1 to 11, wherein the hydrofluorocarbon or hydrochlorofluorocarbon is dichlorotetrafluoropropane, and the fluoroolefin is monochlorotetrafluoropropene.
13. The dichlorotetrafluoropropane is 2,3-dichloro-1,1,1,2-tetrafluoropropane and / or 3,3-dichloro-1,1,1,2-tetrafluoropropane, and the monochlorotetrafluoropropane is The production method according to claim 12, wherein the propene is 1-chloro-2,3,3,3-tetrafluoropropene.