JP7310807B2 - Method for producing (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene - Google Patents

Description

The present invention relates to a method for producing (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene.

Hydrochlorofluorocarbons (HCFCs) are expected to be regulated due to their detrimental effects on the ozone layer. HCFCs include 3,3-dichloro-1,1,1,2,2-pentafluoropropane (CF ₃ —CF ₂ —CHCl ₂ , HCFC-225ca.), 1,3-dichloro-1,1,2, 2,3-pentafluoropropane (CCIF ₂ —CF ₂ —CHFCl, HCFC-225cb.) and the like. With the regulation of HCFCs, development of alternative compounds is desired.

Examples of compounds that can replace HCFC include 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (CHCl=CF-CF ₂ -CF ₂ -CF ₂ H, HCFO-1437dycc (hereinafter referred to as "1437dycc"). 1437dycc has a low global warming potential (GWP) and is expected to be a suitable compound for applications such as cleaning agents, solvents, refrigerants, foaming agents, and aerosols.

In Non-Patent Document 1, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (hereinafter referred to as “OFPO”) is reacted with dichlorotriphenylphosphorane, and 5 -Chloro-1,1,2,2,3,3,4,4-octafluoropentane (HCFC-448occc, hereinafter referred to as "448occc") is obtained, and then 448occc is reacted with sodium methoxide. , 448occc to give 1437dycc.

Zhurnal Organicheskoi Khimii, (Russia), 1988, Vol. 24, No. 8, pp. 1626-1633

By the way, 1437dycc has Z- and E-isomers, which are geometric isomers, depending on the position of the substituent on the double bond. Reaction products obtained by the above conventional methods include (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (hereinafter “1437dycc(Z)” ) and (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (hereinafter referred to as “1437dycc (E)”). .

Depending on the application, either 1437dycc(Z) or 1437dycc(E) may be used alone, or 1437dycc(Z) and 1437dycc(E) may be mixed in a desired ratio and used. However, the difference between the boiling points of 1437dycc (E) and 1437dycc (Z) is small (1437dycc (E) has a boiling point of about 93°C, and 1437dycc (Z) has a boiling point of about 89°C). However, it was difficult to separate 1437dycc(E) and 1437dycc(Z) in the reaction product obtained above.

The present invention has been made to solve the above problems, and is capable of efficiently removing 1437dycc (E) from a composition containing 1437dycc (E) and 1437dycc (Z), It is an object of the present invention to provide a method for producing 1437dycc(Z) with a high recovery rate and an increased purity of 1437dycc(Z).

The present invention provides a method for manufacturing 1437dycc(Z) having the following configuration.
[1] A method for producing 1437dycc(Z), which comprises distilling a distillation composition containing 1437dycc(Z), 1437dycc(E) and water to remove 1437dycc(E) and water.
[2] The production method of [1], wherein 1437dycc(E) and water are removed by forming an azeotropic or azeotrope-like composition.
[3] The production according to [1] or [2], wherein the content of 1437dycc (E) with respect to the total amount of 1437dycc (E) and water in the composition for distillation is 0.01 to 90% by mass. Method.
[4] The production method according to any one of [1] to [3], wherein the content of 1437dycc (Z) with respect to the total amount of the distillation composition is 50% by mass or more.
[5] The production method according to [4], wherein the content of 1437dycc(Z) with respect to the total amount of the distillation composition is 90% by mass or more.
[6] The composition according to any one of [1] to [5], wherein water is added to the mixture containing 1437dycc (Z) and 1437dycc (E) to obtain the composition for distillation, and then distillation is performed. Production method.
[7] Using the reaction composition obtained by dehydrofluorinating 1-chloro-2,2,3,3,4,4,5,5-octafluoropentane to prepare the distillation composition , the production method according to any one of [1] to [6].
[8] Any one of [1] to [7], wherein the distillation is performed using a distillation column under conditions of a top temperature of 10 to 95° C. and an internal pressure of 30 to 760 mmHg. The manufacturing method described in .

In the present specification, with respect to halogenated hydrocarbons, when an abbreviation of the compound is written in parentheses following the name of the compound, the abbreviation is used in place of the name of the compound as necessary. In addition, in the case of a compound having a double bond in the molecule and having an E-isomer and a Z-isomer, the E-isomer and Z-isomer are indicated by (E) or (Z) after the abbreviation of the compound, respectively. A compound name without (E) or (Z) at the end of its abbreviation indicates that it is an E isomer, a Z isomer, or a mixture of E and Z isomers.

According to the method for producing 1437dycc(Z) of the present invention, 1437dycc(E) can be efficiently removed from a composition containing 1437dycc(Z) and 1437dycc(E). Therefore, the recovery rate of 1437dycc(Z) can be increased and the purity of 1437dycc(Z) can be increased.

It is a figure which shows an example of the distillation apparatus used for the manufacturing method of embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.
In the method for producing 1437dycc(Z) of the present embodiment, a distillation composition containing 1437dycc(Z), 1437dycc(E) and water is removed. In the method for producing 1437dycc (Z) of the present embodiment, 1437dycc (Z) is purified by removing 1437dycc (E) and water from the above-described distillation composition, and a composition in which the purity of 1437dycc (Z) is increased can manufacture things. Here, 1437dycc(E) and water in the composition for distillation may be partially or wholly removed.
In the present invention, the 1437dycc(E) and water in the distilling composition are removed from the distilling composition by forming an azeotropic or azeotrope-like composition during distillation of the distilling composition. is preferred.

(Azeotropic composition and azeotrope-like composition)
In general, an azeotropic composition is a mixture of two or more compounds in which the composition of the gas phase produced by vaporization of the liquid phase is the same as the composition of the liquid phase, or The composition of the liquid phase produced will be the same as the composition of the gas phase. Azeotropic compositions are suitable for distillation and reflux because the composition does not change due to evaporation or condensation. In addition, the composition of the azeotropic composition changes depending on the pressure conditions.

Azeotrope-like compositions exhibit behavior similar to azeotrope compositions. That is, the azeotrope-like composition is such that the composition of the gas phase generated by vaporization of the liquid phase is substantially the same as the composition of the liquid phase, or the composition of the liquid phase generated by liquefying the gas phase is the same as the composition of the gas phase. is almost the same as the composition of An azeotrope-like composition can be suitably used for distillation and reflux, like the azeotrope composition, since the composition hardly changes due to evaporation or condensation.

The inventors have found that 1437dycc(E) and water form an azeotropic or azeotrope-like composition. Furthermore, it was found that an azeotropic or azeotrope-like composition consisting of 1437dycc (E) and water is preferentially formed over an azeotropic or azeotrope-like composition consisting of 1437dycc (Z) and water. rice field.

An azeotropic or azeotrope-like composition consisting of 1437dycc(E) and water has a lower boiling point than 1437dycc(Z). That is, the boiling point of 1437dycc(Z) is about 89.degree. In addition, a boiling point is a boiling point under atmospheric pressure. Atmospheric pressure is 101.325 kPa.

Therefore, by forming an azeotropic or azeotrope-like composition consisting of 1437dycc(E) and water, a distillation composition containing 1437dycc(Z), 1437dycc(E) and water can be converted to 1437dycc(E) and water. can be separated from Thereby, 1437dycc(E) and water can be efficiently removed from the distillation composition, the recovery rate of 1437dycc(Z) can be increased, and the purity of 1437dycc(Z) can be increased.

The azeotropic composition consisting of 1437dycc (E) and water has a relative volatility of 1.00 for 1437dycc (E) represented by the following formula (1) under atmospheric pressure, and 1437dycc (E) and water The azeotrope-like composition with has a relative volatility represented by the following formula (1) within the range of 1.00±0.20. The azeotrope-like composition can obtain substantially the same effects as the azeotrope composition, provided that the relative volatility is within the above range.

Relative volatility = (mol% of water in gas phase/mol% of 1437dycc(E) in gas phase)/(mol% of water in liquid phase/mol% of 1437dycc(E) in liquid phase)... (1)

The composition range that allows obtaining the desired relative volatility can be determined as follows. First, the composition of the mixture of 1437dycc(E) and water is gradually changed, and the compositions of the liquid phase and the gas phase are measured with a Karl Fischer moisture meter or gas chromatograph. Using the liquid phase and gas phase compositions, the relative volatility is obtained from the above formula (1). This provides a correlation between composition and relative volatility. From this correlation, the composition that achieves the desired relative volatility can be determined.

In the azeotropic composition and azeotrope-like composition comprising 1437dycc (E) and water, the ratio of the amount of 1437dycc (E) to the total amount of 1437dycc (E) and water is 0.01 to 90% by mass. preferable. When the ratio is within the above range, the relative volatility tends to be within the range of 1.00±0.20, and the boiling point tends to be about 80 to 88°C. From the viewpoint of lowering the boiling point by bringing the relative volatility closer to 1.00, the above ratio is more preferably 0.03 to 70% by mass, more preferably 0.05 to 50% by mass, and 0.05 to 50% by mass. 1 to 30% by mass is particularly preferred.

(Composition for distillation)
The distillation composition contains 1437dycc (Z), 1437dycc (E) and water. The distillation composition is not particularly limited as long as it contains 1437dycc (Z), 1437dycc (E) and water. The distillation composition may also contain ingredients other than 1437dycc(Z), 1437dycc(E) and water. The composition for distillation may be liquid or gaseous.

The distillation composition can be prepared using a reaction composition containing 1437dycc(Z) and 1437dycc(E) produced when 1437dycc(Z) is obtained by the method described later. That is, when 1437dycc (Z) and 1437dycc (E) are contained in the reaction product produced when 1437dycc (Z) is obtained, water can be added to prepare and use a composition for distillation. can. Further, when the reaction product produced when obtaining 1437dycc(Z) contains 1437dycc(Z), 1437dycc(E) and water, this reaction product can be used as it is as a composition for distillation. In addition, the composition after removing acidic substances such as hydrogen fluoride and hydrogen chloride contained in the reaction product by washing with water or alkali is usually added to 1437dycc (Z) and 1437dycc (E). Since it contains water, it can be used as a composition for distillation. In the present invention, "preparing" a composition includes the case of using the reaction composition or the like as it is as the composition.

1437dycc can be obtained, for example, by dehydrofluorinating 448occc in the presence of a base. In the presence of a base, the dehydrofluorination reaction can be carried out in either a liquid phase reaction or a gas phase reaction. Dehydrofluorination reaction in a liquid phase reaction means dehydrofluorination reaction of 448 occc in a liquid state. In addition, dehydrofluorination reaction in a gas phase reaction means dehydrofluorination reaction of 448 occc in gaseous state. From the viewpoint of reaction efficiency, the 448occc dehydrofluorination reaction is preferably carried out in a liquid phase reaction.

The base may be any base capable of performing a dehydrofluorination reaction, and examples thereof include metal hydroxides, metal oxides, metal carbonates, and metal alkoxides. One type of base may be used alone, or two or more types may be used in combination.

Examples of metal hydroxides include alkali metal hydroxides and alkaline earth metal hydroxides. Alkali metal hydroxides include lithium hydroxide, sodium hydroxide and potassium hydroxide. Alkaline earth metal hydroxides include magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide.

Examples of metal oxides include alkali metal oxides and alkaline earth metal oxides. Alkali metal oxides include sodium oxide. Alkaline earth metal oxides include calcium oxide.

Examples of metal carbonates include alkali metal carbonates and alkaline earth metal carbonates. Alkali metal carbonates include lithium, sodium or potassium carbonates. Alkaline earth metal carbonates include beryllium, magnesium, calcium, strontium or barium carbonates.

Examples of metal alkoxides include alkali metal alkoxides. Alkali metal alkoxides include sodium methoxide, sodium ethoxide, potassium methoxide and potassium ethoxide.

As the base, metal hydroxides are preferable, and potassium hydroxide and sodium hydroxide are more preferable, because they are easy to handle and have high reactivity. In particular, when the dehydrofluorination reaction is carried out in a liquid phase reaction, the above metal hydroxides are preferably used because of their high solubility in water.

When the dehydrofluorination reaction is carried out in a liquid phase reaction, it is preferably carried out in the presence of a phase transfer catalyst in order to increase the reaction rate.

Specific examples of the phase transfer catalyst include quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, sulfonium salts, crown ethers, quaternary ammonium salts, quaternary phosphonium salts, quaternary Class arsonium salts and sulfonium salts are preferred, and quaternary ammonium salts are more preferred.

Specific examples of quaternary ammonium salts include tetra-n-butylammonium chloride (TBAC), tetra-n-butylammonium bromide (TBAB), methyltri-n-octylammonium chloride (TOMAC).

Specific examples of quaternary phosphonium salts include tetraethylphosphonium ion, tetra-n-butylphosphonium ion, ethyltri-n-octylphosphonium ion, cetyltriethylphosphonium ion, cetyltri-n-butylphosphonium ion, n-butyltriphenylphosphonium ion. ions, n-amyltriphenylphosphonium ions, methyltriphenylphosphonium ions, benzyltriphenylphosphonium ions or tetraphenylphosphonium ions, and counter ions thereof such as chloride ions, fluoride ions, bromide ions, iodine ions, sulfate ions, nitric acid quaternary phosphonium salts consisting of combinations of ions, phosphate, perchlorate, hydrogen sulfate, hydroxide, acetate, benzoate, benzenesulfonate or p-toluenesulfonate ions. .

Specific examples of quaternary arsonium salts include triphenylmethylarsonium fluoride, tetraphenylarsonium fluoride, triphenylmethylarsonium chloride, tetraphenylarsonium chloride, and tetraphenylarsonium bromide.

Specific examples of sulfonium salts include di-n-butylmethylsulfonium iodide, tri-n-butylsulfonium tetrafluoroborate, dihexylmethylsulfonium iodide, dicyclohexylmethylsulfonium iodide, dodecylmethylethylsulfonium chloride, tris(diethylamino) Sulfonium difluorotrimethyl silicate may be mentioned.

Specific examples of crown ethers include 18-crown-6, dibenzo-18-crown-6 and dicyclohexyl-18-crown-6.

Among the phase transfer catalysts described above, TBAC, TBAB, and TOMAC are preferred from the viewpoints of industrial availability, price, ease of handling, and reactivity.
be.

Moreover, when the dehydrofluorination reaction of 448 occc is carried out in a gas phase reaction, it can be carried out in the presence of activated carbon or a metal catalyst.

The specific surface area of the activated carbon used in the gas phase reaction is preferably 10 to 3000 m ² /g, more preferably 20 to 2500 m ² /g, more preferably 50 to 2000 m ² /g, from the viewpoint of improving the reaction conversion rate and suppressing by-products. g is more preferred. The specific surface area of activated carbon is measured by a method conforming to the BET method.

Specific examples of activated carbon include activated carbon prepared from charcoal, coal, coconut shells, and the like. More specifically, molded coal having a length of about 2 to 5 mm, crushed coal having a mesh of about 4 to 50, granulated coal, and powdered coal can be used.

It is preferable to thoroughly dry the activated carbon before using it in the reaction. The amount of water in the activated carbon is preferably 10% by mass or less, more preferably 5% by mass or less, more preferably 1% by mass, when the total amount of activated carbon and water is 100% by mass from the viewpoint of improving reactivity and selectivity. More preferred are:

Specific examples of metal catalysts include zerovalent iron, zerovalent cobalt, zerovalent nickel, zerovalent palladium, chromium oxide (chromia), aluminum oxide (alumina), zinc oxide, tin oxide, magnesium oxide, oxide Lanthanum, nickel oxide, fluoroaluminum oxide, fluorochrome oxide, magnesium oxide fluoride, lanthanum fluoride oxide, chromium hydroxide, alkali metal halides, and alkaline earth metal halides.

In the dehydrofluorination reaction of 448occc of the above aspect, when the dehydrofluorination reaction is carried out in a gas phase, it is preferable to use activated carbon or an alkaline earth metal fluoride from the viewpoint of improving reactivity and selectivity. , BaF ₂ , SrF ₂ and CaF ₂ are more preferably used.

The reaction product obtained by the dehydrofluorination reaction of 448 occc usually contains water in addition to 1437 dycc when the dehydrofluorination reaction is carried out in a liquid phase reaction. That is, the dehydrofluorination reaction of 448 occc yields a reaction composition containing 1437 dycc (Z), 1437 dycc (E) and water. The reaction composition obtained by the above method may be used as it is as a composition for distillation, or water may be added as appropriate according to the contents of water and 1437dycc (E) contained in the reaction composition. You may use the thing which carried out as a composition for distillation.

The reaction composition contains 1437dycc (Z) and 1437dycc (E) and does not contain water (first reaction composition), 1437dycc (Z), and 1437dycc (E) and water and a reaction composition (second reaction composition).

A distillation composition can be obtained by adding water to the first reaction composition, ie, the reaction composition containing 1437dycc(Z) and 1437dycc(E) and no water.

The second reaction composition, ie, the composition containing 1437dycc(Z), water and 1437dycc(E), can be made as is into the composition for distillation. Water can be added to the second reaction composition according to the contents of water and 1437dycc (E).

The content of 1437dycc (Z) in the distillation composition used in the present embodiment is preferably 50% by mass or more, more preferably 80% by mass or more, relative to the total amount of the distillation composition. 90% by mass or more is more preferable. If the content of 1437dycc(Z) is at least the above lower limit, 1437dycc(E) and water can be efficiently removed.

The respective contents of water and 1437dycc (E) in the distillation composition are not necessarily limited. The inclusion of water and 1437dycc(E) in the distillation composition can form an azeotropic or azeotrope-like composition of water and 1437dycc(E).

It is preferred that all of the 1437dycc(E) and water in the distillation composition form an azeotropic or azeotrope-like composition to be efficiently removed from the distillation composition. From such a viewpoint, the ratio of the content of 1437dycc (E) to the total of the content of 1437dycc (E) and the content of water in the distillation composition is preferably 0.01 to 90% by mass, and 0.01 to 90% by mass. It is more preferably 03 to 70% by mass, even more preferably 0.05 to 50% by mass, and particularly preferably 0.1 to 30% by mass.

The proportion of water in the distillation composition can be adjusted by adding water. For example, if the proportion of water is low, the proportion of water can be increased by adding water.

The distillation composition may contain ingredients other than 1437dycc (Z), 1437dycc (E) and water. As components other than 1437dycc(Z), 1437dycc(E) and water, raw materials for producing 1437dycc(Z) and other than 1437dycc(Z) and 1437dycc(E) produced in the dehydrofluorination reaction of 448occc Examples include by-products. Components other than 1437dycc (Z), 1437dycc (E) and water that can be contained in the distillation composition specifically include 448occc, 1-chloro-3,3,4,4,5,5-hexafluoro -1-pentyne, 3,3,4,4,5,5-hexafluoro-1-pentyne, 1,1,2,2,3,3,4,4,5-nonafluoropentane, 2,3, 3,4,4,5,5-heptafluoro-1-pentene, 1,2,3,3,4,4,5,5-octafluoro-1-pentene, and alcohols such as OFPO and methanol mentioned.

Components other than 1437dycc (Z), 1437dycc (E) and water are preferably 30% by mass or less with respect to the total amount of the distillation composition from the viewpoint of increasing the recovery rate of 1437dycc (Z), and 10 mass % or less. In particular, alcohols such as OFPO and methanol may inhibit the formation of an azeotropic composition of 1437dycc (E) and water. It is preferably 5% by mass or less, more preferably 1% by mass or less.

(distillation)
In the method for producing 1437dycc(Z) of the present embodiment, a composition for distillation containing 1437dycc(Z), 1437dycc(E) and water is distilled. By allowing 1437dycc(E) and water to coexist in the distillation composition, an azeotropic or azeotrope-like composition comprising 1437dycc(E) and water can be formed.

As described above, the boiling point of 1437dycc (Z) is higher than the boiling point of the azeotrope or azeotrope-like composition consisting of 1437dycc (E) and water. At least a portion of the azeotropic or azeotrope-like composition of 1437dycc(E) and water can be removed from the composition for use. The result is a composition with reduced 1437dycc(E) and water content, ie, a composition with increased purity of 1437dycc(Z).

Any known distillation apparatus may be used as long as it can remove at least part of the azeotropic composition or azeotrope-like composition comprising 1437dycc(E) and water from the distillation composition.

FIG. 1 shows an example of a distillation apparatus.
The distillation apparatus 10 has, for example, a distillation column 11. The distillation column 11 includes a pipe 12 for supplying a composition for distillation, a pipe 13 for taking out a distillate from the top of the distillation column 11, and a distillation column. A pipe 14 for taking out the bottom product from the bottom of the column 11 is connected. The distillation apparatus 10 may be either batch type or continuous type. Further, the distillation column 11 may be either hollow type or multi-stage type.

In such a distillation apparatus 10, for example, a distillate containing an azeotropic composition or an azeotrope-like composition consisting of 1437dycc(E) and water can be obtained from the top of the column. A bottom product containing 1437dycc (Z) can also be obtained from the bottom of the column.

In addition, when the distillation composition contains excess 1437dycc (E) or water exceeding the composition range of the azeotropic composition or azeotrope-like composition consisting of 1437dycc (E) and water, these Excess 1437dycc(E) or water may be contained, for example, in bottoms bottoms.

In the case of the multi-stage distillation column 10, the composition for distillation is usually supplied to the middle stage of the multi-stage distillation column 10. In this case, a distillate containing an azeotropic or azeotrope-like composition of 1437dycc(E) and water can be obtained from a stage above the stage to which the distilling composition is fed. Also, the bottoms containing 1437dycc(Z) can be obtained from a stage below the stage to which the distillation composition is fed.

The pressure during distillation is preferably 30 to 760 mmHg, more preferably 100 to 500 mmHg, even more preferably 200 to 400 mmHg in terms of absolute pressure. At such a pressure, the top temperature of the distillation column is preferably 10 to 95°C. By setting the pressure during distillation and the top temperature of the distillation column within the above ranges, at least part of the azeotropic composition or azeotrope-like composition consisting of 1437dycc (E) and water is efficiently removed from the distillation composition. can be removed well.

For example, when the pressure during distillation is 240 mmHg in absolute pressure, the top temperature of the distillation column is 1437 dycc (E) and water. From the viewpoint of increasing the temperature, the temperature is preferably 45°C or higher, more preferably 47°C or higher, and even more preferably 49°C or higher. From the viewpoint of reducing the proportion of 1437dycc(Z) contained in the distillate, the temperature is preferably 57°C or lower, more preferably 55°C or lower, and even more preferably 53°C or lower.

Distillation can be carried out again using the bottoms containing 1437dycc(Z) as the distillation composition. When the bottom product contains 1437dycc (E) and water, distillation can be performed to separate the 1437dycc (E) and water, and to obtain a bottom product with an increased purity of 1437dycc (Z). Obtainable.

Also, a distillate containing 1437dycc (E) and 1437dycc (Z) is used as a distillation composition and distilled again to obtain a bottom product with an increased proportion of 1437dycc (Z). can be done.

In the method for producing 1437dycc(Z) according to the present embodiment, the recovery rate of bottoms can be increased to 85% or more by distillation. The recovery rate of bottoms is preferably 90% or more, more preferably 95% or more. Here, the recovery rate [%] of the bottoms is determined by the following formula from the amount of the distillation composition supplied and the amount of the bottoms recovered.
Recovery rate of bottoms [%] = (amount of bottoms recovered) / (amount of distillation composition supplied) x 100

In addition, in the method for producing 1437dycc(Z) of the present embodiment, the recovery rate of 1437dycc(Z) in the bottom product can be increased to 90% or more by distillation. The recovery rate of 1437dycc(Z) in the bottom product is preferably 93% or more, more preferably 95% or more.

Here, the recovery rate [%] of the bottoms is obtained from the amount of 1437dycc(Z) in the distillation composition and the amount of 1437dycc(Z) in the bottoms by the following formula.

Recovery rate [%] of 1437dycc (Z) in bottoms = (amount of 1437dycc (Z) in bottoms) / (amount of 1437dycc (Z) in distillation composition) x 100

Furthermore, according to such distillation, for example, the ratio of the content of 1437dycc (Z) to the total content of 1437dycc (Z), 1437dycc (E) and water in the bottom product (purity of 1437dycc (Z)) can be 85% by mass or more. The ratio is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, and most preferably 99% by mass or more.

The content of 1437dycc(E) in the bottom product is preferably 2% by mass or less with respect to the total content of 1437dycc(Z), 1437dycc(E) and water.

The water content in the bottoms can be reduced by contacting the bottoms obtained by distillation with a solid adsorbent such as activated carbon or zeolite. The content of water in the bottoms after contact with the solid adsorbent is preferably 200 ppm or less with respect to the total content of 1437dycc(Z), 1437dycc(E) and water.

The present invention will be described in detail below with reference to examples. However, the present invention is not limited by these examples.

(Example 1)
448 occc and tetra-n-butylammonium bromide (TBAB) were placed in a reactor, 34% by mass potassium hydroxide (KOH) aqueous solution was added dropwise, and 448 occc dehydrofluorination reaction was performed at 30°C. After reacting for 8 hours, the organic layer was recovered to obtain a composition for distillation.
As a distillation column, a multi-stage distillation column having 50 theoretical plates was prepared. A composition for distillation was supplied at a rate of 1.0 kg/h from the 20th stage from the top of the distillation column. The distillation composition contains 0.9490 kg/h of 1437dycc(Z), 0.0500 kg/h of water, and 0.0010 kg/h of 1437dycc(E), as shown in Table 1. Thereafter, continuous distillation was carried out with an operating pressure of 240 mmHg and a tower top temperature of 52.0±0.5°C.

During the distillation, a distillate was withdrawn from the top of the tower and a bottom product was withdrawn from the bottom of the tower. Then, with respect to the distillate and the bottom product, a Karl Fischer moisture meter was used to determine the amount of water recovered, and gas chromatography was used to determine the amount of 1437dycc (Z) and 1437dycc (E) recovered. Also, the recovery rate (collected amount/supplied amount) was obtained from the supplied amount and the collected amount.

Table 1 shows the amount of the distillation composition supplied and the amount and rate of recovery of the distillate and the bottom product, respectively. In addition, Table 2 shows the composition for distillation, the distillate and the bottom product.

In addition, the composition of the composition for distillation is obtained from the supply amount of each component. The composition of the distillate and the bottom product is obtained from the recovered amount of each component.

As is clear from Tables 1 and 2, by using a distillation composition containing 1437dycc (Z), 1437dycc (E) and water, the bottom product recovery rate can be 93% by mass or more. Together with this, the content ratio of 1437dycc(Z) in the can product can be 99% by mass or more.

(Example 2)
As shown in Table 3, distillation and measurement were carried out in the same manner as in Example 1 by changing the supply amount of each component in the composition for distillation. Table 3 shows the recovery amount and recovery rate of distillate and bottom product, respectively. In addition, Table 4 shows the composition of the distillation composition, the distillate and the bottom product, respectively.

As is clear from Tables 3 and 4, by using a distillation composition containing 1437dycc (Z), 1437dycc (E) and water, the bottom product recovery rate can be 93% by mass or more. Together with this, the content ratio of 1437dycc(Z) in the can product can be 99% by mass or more.

According to the present invention, 1437dycc(E) can be efficiently removed from a composition containing 1437dycc, the recovery rate of 1437dycc(Z) can be increased, and the purity of 1437dycc(Z) can be increased. Therefore, 1437dycc(Z) can be effectively used in a wide range of fields such as detergents, solvents, and refrigerants.
In addition, the entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2018-103780 filed on May 30, 2018 are cited here, and as a disclosure of the specification of the present invention, It is taken in.

10... Distillation apparatus, 11... Distillation column, 12, 13, 14... Piping.

Claims (10)

(Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, (E)-1-chloro-2,3,3,4,4,5,5 - distilling a distillation composition containing heptafluoro-1-pentene and water to obtain (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene and characterized by removing water ,
(E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene and water are removed by forming an azeotropic or azeotrope-like composition; A method for producing (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene. (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, (E)-1-chloro-2,3,3,4,4,5,5 - distilling a distillation composition containing heptafluoro-1-pentene and water to obtain (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene and characterized by removing water ,
In the distillation composition, (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene and (E)-1-chloro-2 relative to the total amount of water , 3,3,4,4,5,5-heptafluoro-1-pentene content is 0.01 to 90% by mass , (Z)-1-chloro-2,3,3,4, A method for producing 4,5,5-heptafluoro-1-pentene. (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, (E)-1-chloro-2,3,3,4,4,5,5 - distilling a distillation composition containing heptafluoro-1-pentene and water to obtain (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene and characterized by removing water ,
The content of (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene with respect to the total amount of the distillation composition is 50% by mass or more , (Z )-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene. The content of (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene with respect to the total amount of the distillation composition is 90% by mass or more, according to claim 3. The manufacturing method according to 3 . (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene and water are removed by forming an azeotropic or azeotrope-like composition; The production method according to any one of claims 2-4. In the distillation composition, (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene and (E)-1-chloro-2 relative to the total amount of water , 3,3,4,4,5,5-heptafluoro-1-pentene content is 0.01 to 90% by mass, the production method according to claim 3 or 4. (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene and water are removed by forming an azeotropic or azeotrope-like composition;
In the distillation composition, (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene and (E)-1-chloro-2 relative to the total amount of water , 3,3,4,4,5,5-heptafluoro-1-pentene content is 0.01 to 90% by mass, the production method according to claim 3 or 4. (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene and (E)-1-chloro-2,3,3,4,4,5,5 -The production method according to any one of claims 1 to 7 , wherein water is added to the mixture containing heptafluoro-1-pentene to obtain the composition for distillation, and then distillation is performed. The composition for distillation is prepared using a reaction composition obtained by dehydrofluorinating 1-chloro-2,2,3,3,4,4,5,5-octafluoropentane. 9. The production method according to any one of 1 to 8 . The distillation according to any one of claims 1 to 9 , wherein the distillation is performed using a distillation column, and the distillation conditions of the distillation column are a tower top temperature of 10 to 95 ° C. and a tower internal pressure of 30 to 760 mmHg. Production method.

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