JPWO2020149365A1 - Method for Producing Z-1,2-Dichloro-3,3,3-Trifluoropropene - Google Patents

Abstract

The present invention includes (Z) -1,2-dichloro-3,3,3-trifluoropropene (1223xd (Z)) and 1,1-dichloro-3,3,3-trifluoropropene (1223za). It is an object of the present invention to provide a method for producing 1223xd (Z) from a composition easily and at low cost. One of the embodiments of the present invention is a method for producing (Z) -1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (Z)). In this method, a composition containing 1223xd (Z) and 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za) is brought into contact with a base to form 1223xd (Z) in the composition. Includes reducing the 1223za ratio to.

Description

The present invention relates to a method for producing (Z) -1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (Z)).

1,2-Dichloro-3,3,3-trifluoropropene (HCFO-1223xd), which is a type of hydrochlorofluoroolefin (HCFO), is a solvent, cleaning agent, and refrigerant as an alternative to hydrofluorocarbons (HFCs). Etc. are expected (for example, Patent Documents 1 to 8). In 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), trans isomers (E isomers) and cis isomers (Z isomers) are present (hereinafter, each is HCFO-). 1223xd (E), sometimes referred to as HCFO-1223xd (Z)). More suitable uses may differ depending on the geometrical isomers. For example, high purity HCFO-1223xd (Z) is expected to be suitable for certain refrigerant applications.

Japanese Unexamined Patent Publication No. 2-221388 Japanese Unexamined Patent Publication No. 2-221389 Japanese Unexamined Patent Publication No. 2-221962 Japanese Unexamined Patent Publication No. 2-22469 Japanese Unexamined Patent Publication No. 2-22496 Japanese Unexamined Patent Publication No. 2-22497 Japanese Unexamined Patent Publication No. 2-222702 Japanese Unexamined Patent Publication No. 2013-87187

As disclosed in Japanese Patent Application No. 2018-141359, (Z) -1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (Z)) and 1,1-dichloro-3. , 3,3-Trifluoropropene (HCFO-1223za) was found to form an azeotropic composition. This azeotropic composition is useful in a variety of applications. On the other hand, once the azeotropic composition is formed, it is difficult to separate the components constituting the azeotropic composition. Apart from the usefulness of the azeotropic composition itself, high-purity HCFO-1223xd (Z) may be required depending on the application. As one method for meeting the demand, a method for efficiently obtaining high-purity HCFO-1223xd (Z) from this azeotropic composition has been sought.

The present invention relates to (Z) -1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (Z)) and 1,1-dichloro-3,3,3-trifluoropropene (HCFO-). It is an object of the present invention to provide a method for easily and inexpensively producing HCFO-1223xd (Z) having a reduced HCFO-1223za content from a composition containing 1223za).

One embodiment of the present invention comprises contacting a composition containing 1223xd (Z) with 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za) with a base to make the composition. It is a method for producing HCFO-1223xd (Z), which comprises reducing the ratio of HCFO-1223za to HCFO-1223xd (Z) in the medium.

In the above method, the base may be at least one selected from compounds containing alkali metals or alkaline earth metals, ammonia, and amines.

In the above method, the base is an alkali metal alkoxide, an alkali metal carbonate, an alkali metal hydroxide, an alkaline earth metal carbonate, an alkaline earth metal hydroxide, an alkali metal carboxylate, and an alkali. It may be at least one selected from the carbonates of earth metals.

In the above method, contact with the base may be carried out at a temperature of 10 ° C to 60 ° C.

In the above method, the composition is trichlorotrifluoropropane (HCFC-233), tetrachlorotrifluoropropane (HCFC-223), pentachlorotrifluoropropane (CFC-213), monochlorotrifluoropropene (HCFO-1233), and the like. At least one selected from dichlorotrifluoropropene (HCFO-1223), trichlorotrifluoropropene (CFO-1213), 1-chloro-3,3,3-trifluoroproppine, hydrogen fluoride, hydrogen chloride, chlorine and water. It may contain a compound.

According to the present invention, (Z) -1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (Z)) and 1,1-dichloro-3,3,3-trifluoropropene (HCFO-). From the composition containing 1223za), HCFO-1223xd (Z) having a reduced HCFO-1223za content can be easily produced at low cost.

Hereinafter, the method according to the embodiment of the present invention will be described. However, the present invention can be carried out in various embodiments without departing from the gist thereof, and is not construed as being limited to the description contents of the embodiments exemplified below. In addition, even if the action and effect are different from the action and effect brought about by the following embodiments, those which are clear from the description of the present specification or which can be easily predicted by those skilled in the art are of course. It is understood that it was brought about by the present invention.

In the present embodiment, a method for producing (Z) -1,2-dichloro-3,3,3-trifluoropropene (hereinafter, also referred to as "1223xd (Z)") (hereinafter, also simply referred to as "the present production method"). (Note) will be explained.

In the present production method, a composition containing 1223xd (Z) and 1,1-dichloro-3,3,3-trifluoropropene (hereinafter, also referred to as "1223za") is contacted with a base (hereinafter, simply "the main contact"). ”). By this contact, 1223za in the composition reacts with the base and is decomposed. Thereby, the ratio of 1223za to 1223xd (Z) in the composition can be reduced. Although 1223xd (Z) can also react with the base, the inventors of the present application have found that 1223za reacts preferentially with the base.

(Composition containing 1223xd (Z) and 1223za)
In this production method, a composition containing 1223xd (Z) and 1223za is used. The content ratio of 1223xd (Z) and 1223za in this composition is not particularly limited. For example, the molar ratio of 1223xd (Z) to 1223za is expressed as 1223za / 1223xd (Z), 0.0001 to 10000, 0.0001 to 1000, 0.0001 to 100, 0.0001 to 10, 0.0001. It may be ~ 1, 0.0001 to 0.1, 0.0001 to 0.01, 0.0001 to 0.001.

Further, the composition may contain components other than 1223xd (Z) and 1223za. The total content ratio of 1223xd (Z) and 1223za in this composition is not particularly limited. When this composition contains components other than 1223xd (Z) and 1223za, for example, the total content of 1223xd (Z) and 1223za in the composition is 1% by mass or more, 10% by mass or more, and 30% by mass or more. It may be 50% by mass or more, more than 50% by mass, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more.

When this composition contains components other than 1223xd (Z) and 1223za, the components are not particularly limited, and examples thereof include raw materials and by-products used in the process of producing 1223xd (Z) and 1223za. Examples of the components other than 1223xd (Z) and 1223za include trichlorotrifluoropropane (hereinafter, also referred to as “HCFC-233”), tetrachlorotrifluoropropane (hereinafter, also referred to as “HCFC-223”), and pentachlorotri. Fluoropropane (hereinafter, also referred to as "CFC-213"), monochlorotrifluoropropene (hereinafter, also referred to as "HCFO-1233"), dichlorotrifluoropropene (hereinafter, also referred to as "HCFO-1223"), trichlorotrifluoropropene. (Hereinafter, also referred to as "CFO-1213"), 1-chloro-3,3,3-trifluoropropene, hydrogen fluoride, hydrogen chloride, chlorine, water and the like may be used.

Examples of HCFC-233 include 1,1,2-trichloro-3,3,3-trifluoropropane (HCFC-233da) and 1,2,2-trichloro-3,3,3-trifluoropropane (HCFC). -233ab) and the like.

Examples of HCFC-223 include 1,1,2,2-tetrachloro-3,3,3-trifluoropropane (HCFC-223aa) and 1,2,2,3-tetrachloro-1,3,3. -Trifluoropropane (HCFC-223ab), 1,1,1,2-tetrachloro-3,3,3-trifluoropropane (HCFC-223db) and the like can be mentioned.

Examples of CFC-213 include 1,1,1,2,2-pentachloro-3,3,3-trifluoropropane (CFC-213ab) and 1,1,2,2,3-pentachloro-1,3. , 3-Trifluoropropane (CFC-213aa) and the like.

Examples of HCFO-1233 include (E) -1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)) and (Z) -1-chloro-3,3,3-trifluoro. Propene (HCFO-1233zd (Z)), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), (E) -1-chloro-2,3,3-trifluoro-1-propene (E) HCFO-1233yd (E)), (Z) -1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (Z)) and the like can be mentioned.

The HCFO-1223 is a dichlorotrifluoropropene other than 1223xd (Z) and 1223za. For example, (E) -1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (E)). And so on.

Examples of the CFO-1213 include 1,1,2-trichloro-3,3,3-trifluoropropene (CFO-1213xa).

(base)
The base used in this production method is preferably at least one selected from compounds containing alkali metals or alkaline earth metals, ammonia, and amines. Here, the alkali metal means lithium, sodium, potassium, rubidium or cesium, and the alkaline earth metal means magnesium, calcium or strontium.

Compounds containing alkali metals or alkaline earth metals include, for example, alkali metal alkoxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, alkali metals. Hydroxide, alkali earth metal hydroxide, alkali metal carboxylate, alkaline earth metal carboxylate and the like.

As the amine, for example, a primary amine ^{represented by the general formula R 1-} NH ₂ , an acyclic secondary amine represented by the general formula R ² (R ³ ) -NH, and a cyclic amine may be used. Can be done. Here, R ¹ , R ² , and R ³ are independently alkyl groups, aryl groups, or alicyclic hydrocarbon groups, respectively.

The base may be, for example, a compound selected from the following group:
Alkaline metal alkoxides such as sodium methoxydo and sodium ethoxydo; Alkaline metal carbonates such as sodium carbonate, potassium carbonate, lithium carbonate and calcium carbonate; Alkaline metal hydrogen carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate and lithium hydrogen carbonate Salts; hydroxides of alkali metals such as potassium hydroxide, sodium hydroxide, calcium hydroxide; hydroxides of alkaline earth metals such as magnesium hydroxide; carboxylates of alkali metals such as sodium acetate and potassium acetate; Lower alkylamines such as methylamine, ethylamine and propylamine, aromatic amines such as aniline and toluidine; dilower alkylamines such as dimethylamine, diethylamine and dipropylamine, aromatics such as N-methylaniline and N-methyltoluidine. Secondary amines; pyrrolidine, piperidine, piperazine, morpholin, quinuclidine, 1,4-diazabicyclo [2.2.2] octane (DABCO), pyrrol, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, oxazole, thiazole, rutidin , Diazabicycloundecene (DBU), Diazabicyclononene (DBN) and the like cyclic amines.

From the viewpoint of economy and ease of handling, the base is particularly preferably alkali metal carbonate, alkaline earth metal carbonate, alkali metal hydroxide, alkaline earth metal hydroxide, and alkali metal water. Oxides are even more preferred.

The amount of the base used in this contact is at least 1 equivalent with respect to 1223za1 equivalent, but one may be used in excess of the other. In one embodiment, it is preferable to use an amount of base in excess of 1223za, for example, 1 equivalent to 100 equivalents or less, 1 equivalent to 60 equivalents or less, or 1 equivalent to 40 equivalents or less with respect to 1 equivalent of 1223 z. can.

(solvent)
This contact may be performed in the presence of a solvent. Examples of the solvent include alkanes such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, and halogenated hydrocarbons such as dichloromethane and chloroform. Ketones such as hydrogens, acetone, methyl ethyl ketone, methyl isobutyl ketone, nitriles such as acetonitrile, propionitrile, butyl nitrile, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), hexamethyl Amidos such as phosphoric triamide (HMPA), glycols such as ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, and ethylene glycol monoacetate, water and the like can be used. The solvent may be used alone or in combination of two or more.

This contact may be performed in the presence of additives such as a compatibilizer and a phase transfer catalyst. Examples of the compatibilizer include alcohols such as methanol, ethanol and propanol. Examples of the phase transfer catalyst include crown ether, cryptonde, onium salt and the like.

Further, this contact may be carried out in the presence of both a solvent and an additive.

(Contact method)
In this contact, the composition containing 1223xd (Z) and 1223za may be in a gaseous or liquid state, and the base may be in a gaseous, liquid or solid state. The main contact is preferably liquid-liquid contact or gas-liquid contact. When the base is a solid, it may be used as a solution using the above-mentioned solvent for contact with the composition containing 1223xd (Z) and 1223za. The concentration of the solution is not particularly limited, but it is preferable to be appropriately adjusted by those skilled in the art according to the type of the base so that the reaction between 1223za and the base proceeds and the base is dissolved in the solvent. For example, when an aqueous solution of an alkali metal hydroxide is used, the content of the alkali metal hydroxide in the aqueous solution is 0.5% by mass to 85% by mass, preferably 0.5% by mass to 50% by mass. It is preferably 1% by mass to 40% by mass.

The pressure in this contact is not particularly limited, and can be performed under normal pressure or pressurized conditions. For example, it can be carried out at 0.1 MPa to 2 MPa (absolute pressure reference; the same applies hereinafter) or 0.1 MPa to 0.5 MPa.

The temperature in the main contact is not particularly limited, but the main contact is preferably performed in a liquid-liquid state or a gas-liquid state. Depending on the pressure, for example, it can be carried out at −20 ° C. to + 60 ° C., preferably 10 ° C. to 60 ° C.

This contact can be performed continuously, semi-continuously or in batch. Further, in this production method, the material of the reaction vessel is not particularly limited. For example, a reaction vessel made of general stainless steel, glass, fluororesin, glass, a material lined with fluororesin, or the like can be used.

The purification operation after the main contact is not particularly limited, and for example, 1223xd (Z) can be purified by performing a distillation operation, drying, or the like.

By this production method, the content of 1223za is reduced from the composition containing 1223xd (Z) and 1223za, and high-purity 1223xd (Z) can be produced.

Hereinafter, embodiments of the present invention will be described in detail by way of examples, but the embodiments of the present invention are not limited to the examples described below. In the examples described below, "%" of the composition analysis value represents the area% of the composition obtained by measuring by gas chromatography (device: GC-2010Plus (Shimadzu Corporation), detector: FID). Further, the "1223za ratio" means a value obtained by dividing the 1223za area% in the composition by the 1223xd (Z) area%.

[Example 1]
A composition containing 1223xd (Z) 98.33% and 1223za 1.55% (ratio of 1223za = 0.0158) 5 g, 1 in a 100 mL pressure-resistant container made of SUS316 equipped with a stirring blade coated with tetrafluoroethylene resin. 50 g of a mass% potassium hydroxide aqueous solution (equivalent to 1223 za in the composition: 19) was added, and the mixed solution in the pressure-resistant container was stirred at 30 ° C. for 22 hours in a closed state. After the stirring was completed, the pressure-resistant container was cooled and the organic layer was taken out. The organic layer was washed with 50 g of water and then analyzed by gas chromatography to calculate the ratio of 1223za to 1223xd (Z) in the composition after the contact reaction. Then, the 1223za reduction rate [%] was calculated from the ratio of 1223za to 1223xd (Z) in the composition before the contact reaction and the ratio of 1223za after the contact reaction according to the following formula 1.
1223za reduction rate [%] = [(1223za ratio before contact reaction-1223za ratio after contact reaction) / (1223za ratio before contact reaction)] × 100 ... (Equation 1)

[Example 2]
Using 30 g of a composition containing 1223xd (Z) 98.33% and 1223za 1.55% (ratio of 1223za = 0.0158) and 30 g of a 10% by mass potassium hydroxide aqueous solution, the mixture was stirred at 50 ° C., and the organic substance after stirring was completed. The same operation as in Example 1 was performed except that the layer was washed with 30 g of water. The 1223za reduction rate [%] was calculated in the same manner as in Example 1.

[Example 3]
In a 100 mL three-necked flask, 5 g of a composition containing 1223xd (Z) 98.33% and 1223za 1.55% (ratio of 1223za = 0.0158) and 50 g of a 1% by mass potassium hydroxide aqueous solution were placed and 22 at 0 ° C. Stirred for hours. After the reaction, the organic layer was taken out, washed with 50 g of water, and then the organic layer was analyzed by gas chromatography. The 1223za reduction rate [%] was calculated in the same manner as in Example 1.

The results of Examples 1 to 3 are shown in Tables 1 and 2. In Table 1, the numerical value in parentheses () after the composition analysis value [%] of 1223za indicates the ratio of 1223za to 1223xd (Z), and is described after the composition analysis value [%] of owners. The numerical value in) shows the ratio of others (a compound (group) other than 1223xd (Z) and 1223za) to 1223xd (Z).

As shown in Table 2, it was confirmed that when the composition containing 1223xd (Z) and 1223za was brought into contact with the base, 1223za reacted preferentially with the base over 1223xd (Z). Above all, it was found that when the temperature of the contact reaction was 30 ° C. and 50 ° C., a high 1223za reduction rate was exhibited.

Further, the same operation as in Example 2 is performed except that a 10% sodium hydroxide aqueous solution (equivalent to 1223 za in the composition: 3) is used instead of the 10 mass% potassium hydroxide aqueous solution. Is also considered to show a high 1223za reduction rate similar to that of Example 2.

Claims (5)

(Z) A composition containing -1,2-dichloro-3,3,3-trifluoropropene and 1,1-dichloro-3,3,3-trifluoropropene is brought into contact with a base to prepare the composition. Includes reducing the proportion of 1,1-dichloro-3,3,3-trifluoropropene to (Z) -1,2-dichloro-3,3,3-trifluoropropene in (Z)-. A method for producing 1,2-dichloro-3,3,3-trifluoropropene. The method according to claim 1, wherein the base is at least one selected from a compound containing an alkali metal or an alkaline earth metal, ammonia, and an amine. The bases are alkali metal alkoxides, alkali metal carbonates, alkali metal hydroxides, alkaline earth metal carbonates, and alkaline earth metal hydroxides, alkali metal carboxylates, alkaline earth metals. The method according to claim 1, which is at least one selected from carbonates. The method according to any one of claims 1 to 3, wherein the contact with the base is carried out at a temperature of 10 ° C to 60 ° C. The composition is trichlorotrifluoropropane, tetrachlorotrifluoropropane, pentachlorotrifluoropropane, monochlorotrifluoropropene, dichlorotrifluoropropene, trichlorotrifluoropropene, 1-chloro-3,3,3-trifluoropropene, The method according to any one of claims 1 to 4, which comprises at least one compound selected from hydrogen fluoride, hydrogen chloride, chlorine and water.