WO2018193884A1 - Method for producing 1,1-dichloro-3,3,3-trifluoropropene - Google Patents

Abstract

The method for producing 1,1-dichloro-3,3,3-trifluoropropene (1223za) according to the present invention is characterized by comprising a step in which 1,1,3,3,3-pentachloropropene (1220za) is fluorinated with hydrogen fluoride to produce 1,1,-dichloro-3,3,3-trifluoropropene (1223za). By the method, 1223za can be efficiently produced from 1220za as a starting material.

Description

Process for producing 1,1-dichloro-3,3,3-trifluoropropene

The present invention relates to a method for producing 1,1-dichloro-3,3,3-trifluoropropene (CCl ₂ ═CHCF ₃ ; hereinafter also referred to as 1223za). The present invention also relates to a method for co-producing 1223za and 1,1,3-trichloro-3,3-difluoropropene (CCl ₂ = CHCCClF ₂ ; hereinafter also referred to as 1222za) and a method for producing 1222za. Furthermore, the present invention provides a method for co-producing 1223za and 1,1-dichloro-1,3,3,3-tetrafluoropropane (CCl ₂ FCH ₂ CF ₃ ; hereinafter also referred to as 234fb), and produces 234fb. Regarding the method.

Hydrofluoroolefins (hereinafter also referred to as HFO compounds) are hydrochlorofluorocarbons such as 1,3,3-dichloro-1,1,2,2,2-pentafluoropropane (CCIF ₂ CF ₃ CH ₂ Cl; 225ca) ( Since it has a lower global warming potential (GWP) than HCFC compounds and is friendly to the global environment, if it can be used commercially, it is being replaced by various uses such as solvents. 1223za is also a kind of HFO compound.

Various methods are known as a method for producing 1223za. For example, Patent Document 1 describes a method for producing various fluorinated propenes. Among them, in Ex2G of Example II, trichlorethylene (CCl ₂ = CHCl; HCO-1120) and trifluoromethane (CHF ₃ ; R— A method for producing 1223za by reacting 32) at 400 ° C. has been reported. However, the reaction according to Patent Document 1 is carried out under a gas phase reaction and a high temperature condition, and the conversion rate of the raw material is around 12%, which is not suitable for mass production.

Non-Patent Document 1 discloses that 1,1,3,3,3-pentachloropropene (CCl ₂ = CHCCl ₃ ; hereinafter also referred to as 1220za) is reacted with antimony fluoride (SbF ₃ ) in a liquid phase reaction. To produce 1223za. However, in the method of Non-Patent Document 1, expensive SbF ₃ is used in a stoichiometric amount or more, which is not suitable for mass production on an industrial scale.

Patent Document 2 discloses that 1,231-za is obtained by reacting a base with 1,1,1-trifluoro-3,3,3-trichloropropane (CF ₃ CH ₂ CCl ₃ ; HCFC-233fb). A method of manufacturing is described. However, in the method of Patent Document 2, although 1223za is obtained with high yield and high selectivity, a large amount of basic waste water or organic base is discharged in the post-treatment.

There is still a need for development of a method for efficiently producing 1223za (a method for producing 1223za that is industrially easy to adopt).

Japanese Patent No. 5706432 JP 2016-79101 A

The present invention has been made from the above viewpoint, and an object of the present invention is to provide an efficient method for producing 1223za. Another object of the present invention is to provide an efficient method for co-production of 1223za and 1222za and an efficient method for producing 1222za. Furthermore, an object of the present invention is to provide an efficient method for co-production of 1223za and 234fb and an efficient method for producing 234fb.

The present inventors have intensively studied to solve the above problems. As a result, it was found that 1223za can be produced by fluorinating 1220za using hydrogen fluoride as a fluorinating agent, and the present invention has been completed.

Further, the present inventors have found that 1223za and 1222za can be produced in parallel by fluorinating 1220za using hydrogen fluoride as a fluorinating agent, and that 1222za can be produced, and the present invention has been completed. It was.

Furthermore, the present inventors have found that 1223za and 234fb can be produced in parallel by fluorinating 1220za using hydrogen fluoride as a fluorinating agent, and that 234fb can be produced, thereby completing the present invention. It was.

That is, the present invention includes the following inventions.

[Invention 1]
And fluorinating 1,1,3,3,3-pentachloropropene with hydrogen fluoride to produce 1,1-dichloro-3,3,3-trifluoropropene. , 1-Dichloro-3,3,3-trifluoropropene production method.

[Invention 2]
The method according to claim 1, wherein the amount of hydrogen fluoride used is 3 to 40 mol per mol of 1,1,3,3,3-pentachloropropene.

[Invention 3]
The method according to claim 1 or 2, wherein the fluorination is performed in a liquid phase.

[Invention 4]
The method according to invention 3, wherein the fluorination is carried out at 0 to 200 ° C.

[Invention 5]
By the fluorination, 1,1-dichloro-3,3,3-trifluoropropene and 1,1,3-trichloro-3,3-difluoropropene or 1,1-dichloro-1,3,3,3 -Process according to invention 3 or 4, characterized in that tetrafluoropropane is produced.

[Invention 6]
The method according to claim 1 or 2, wherein the fluorination is performed in a gas phase.

[Invention 7]
The method according to claim 6, wherein the fluorination is performed at 100 to 500 ° C.

[Invention 8]
The method according to any one of inventions 1 to 7, wherein the fluorination is carried out at 0 to 10 MPaG.

[Invention 9]
The method according to any one of inventions 1 to 8, wherein the fluorination is carried out in the presence or absence of a catalyst.

[Invention 10]
The method according to any one of inventions 1 to 9, comprising a step of purifying 1,1-dichloro-3,3,3-trifluoropropene.

[Invention 11]
Together with 1,1,3,3,3-pentachloropropene, 1,1,3,3-tetrachloro-3-fluoropropene or 1,1,3-trichloro-3,3-difluoropropene is used for the fluorination. A method according to any one of inventions 1 to 10, wherein the method is provided.

[Invention 12]
Fluorinating 1,1,3,3,3-pentachloropropene with hydrogen fluoride to produce 1,1,3-trichloro-3,3-difluoropropene, A method for producing 1,3-trichloro-3,3-difluoropropene.

[Invention 13]
Process according to invention 12, characterized in that the fluorination is carried out in the liquid phase.

[Invention 14]
The method according to the invention 12 or 13, characterized in that the fluorination is carried out in the presence or absence of a catalyst.

[Invention 15]
Inventions 12 to 14 are characterized in that 1,1-dichloro-3,3,3-trifluoropropene is produced together with 1,1,3-trichloro-3,3-difluoropropene by the fluorination. The method in any one of.

[Invention 16]
Dehydrochlorination of 1,1,1,3,3,3-hexachloropropane in the liquid phase to obtain 1,1,3,3,3-pentachloropropene in the presence of a Lewis acid catalyst The method according to any one of inventions 1 to 15, further comprising a crystallization step.

[Invention 17]
Chlorination of 1,1,1,3,3-pentachloropropane in the liquid phase to give 1,1,1,3,3,3-hexachloropropane under UV irradiation or in the presence of a radical initiator The method according to invention 16, further comprising a crystallization step.

In a preferred embodiment of the present invention, 1,1,3,3,3-pentachloropropene (1220za) is reacted with hydrogen fluoride to fluorinate 1220za. By the fluorination, 1,1-dichloro-3,3,3-trifluoropropene (1223za) is produced. In the fluorination, the amount of hydrogen fluoride used is 3 to 40 moles, preferably 4 to 35 moles, and particularly preferably 8 to 30 moles per mole of 1220za. The fluorination is performed at 0.1 to 10 MPaG (referred to as gauge pressure, hereinafter the same in this specification), preferably 0.15 to 6 MaG, particularly preferably more than 0.25 MPaG and 4.5 MPaG. It is as follows. The fluorination is carried out in the presence or absence of a catalyst, preferably in the absence of a catalyst. The fluorination is performed in the presence or absence of a solvent, preferably in the absence of a solvent. Further, the fluorination may be carried out by a batch type, semi-continuous flow type or continuous flow type, and preferably by a continuous flow type. The fluorination is performed in a liquid phase or a gas phase. The fluorination in the liquid phase is performed at 0 to 200 ° C., preferably 35 to 200 ° C., particularly preferably 35 to 140 ° C., and further preferably 40 to 130 ° C. The fluorination in the gas phase is performed at 100 to 500 ° C., preferably 150 to 400 ° C., particularly preferably 200 to 350 ° C. Further, by the above fluorination, 1,1,3,3-tetrachloro-3-fluoropropene (hereinafter also referred to as 1221za), 1,1,3-trichloro-3,3-difluoropropene (1222za) together with 1223za 1,1-dichloro-1,3,3,3-tetrafluoropropane (234fb), 1,1,1,3,3-pentafluoropropane (CF ₃ CH ₂ CHF ₂ ; hereinafter also referred to as 235fa), 1,1,1,3,3,3-hexafluoropropane (CF ₃ CH ₂ CF ₃ ; hereinafter also referred to as 236fa) may be produced. Moreover, it is preferable to refine | purify 1223za obtained by the said fluorination. Moreover, the produced by-product can be separated and subjected to the fluorination together with 1220za.

In a preferred embodiment of the present invention, 1,1,3,3,3-pentachloropropene (1220za) and hydrogen fluoride are reacted to fluorinate 1220za. By the fluorination, 1,1,3-trichloro-3,3-difluoropropene (1222za) is produced. In the fluorination, the amount of hydrogen fluoride used is 2 to 40 moles, preferably 3 to 35 moles, and particularly preferably 4 to 30 moles per mole of 1220za. The fluorination is performed at 0.1 to 10 MPaG, preferably 0.1 to 3 MaG, and particularly preferably 0.1 to 2 MPaG. The fluorination is carried out in the presence or absence of a catalyst, preferably in the absence of a catalyst. The fluorination is performed in the presence or absence of a solvent, preferably in the absence of a solvent. Further, the fluorination may be carried out by a batch type, semi-continuous flow type or continuous flow type, and preferably by a continuous flow type. The fluorination is preferably performed in a liquid phase. The fluorination is preferably carried out at 0 to 70 ° C., particularly preferably 0 to 60 ° C., further preferably 10 to 55 ° C. In addition, by the fluorination, 1,1,3,3-tetrachloro-3-fluoropropene (1221za), 1,1-dichloro-3,3,3-trifluoropropene (1223za), 1,222za, 1-dichloro-1,3,3,3-tetrafluoropropane (234fb) and the like may be produced. Moreover, it is preferable to refine | purify 1222za obtained by the said fluorination. Moreover, 1222za obtained by the said fluorination can also be used for the said fluorination with 1220za.

In a preferred embodiment of the present invention, 1,1,3,3,3-pentachloropropene (1220za) and hydrogen fluoride are reacted to fluorinate 1220za. By the fluorination, 1,1-dichloro-3,3,3-trifluoropropene (1223za) and 1,1,3-trichloro-3,3-difluoropropene (1222za) are produced together. In the fluorination, the amount of hydrogen fluoride used is 3 to 40 moles, preferably 4 to 35 moles, and particularly preferably 8 to 30 moles per mole of 1220za. The fluorination is preferably carried out at 0 to 70 ° C., particularly preferably 0 to 60 ° C., further preferably 10 to 55 ° C. The fluorination is performed at 0.1 to 10 MPaG, preferably 0.1 to 3 MaG, and particularly preferably 0.1 to 2 MPaG. The fluorination is carried out in the presence or absence of a catalyst, preferably in the absence of a catalyst. The fluorination is performed in the presence or absence of a solvent, preferably in the absence of a solvent. Further, the fluorination may be carried out by a batch type, semi-continuous flow type or continuous flow type, and preferably by a continuous flow type. The fluorination is preferably performed in a liquid phase. The fluorination may produce 1,1-dichloro-1,3,3,3-tetrafluoropropane (234fb) together with 1223za and 1222za. Moreover, it is preferable to refine | purify 1223za and 1222za obtained by the said fluorination. The co-produced 1223za and 1222za can be separated and used for various purposes, and 1222za can be used for fluorination together with 1220za.

In a preferred embodiment of the present invention, 1,1,3,3,3-pentachloropropene (1220za) and hydrogen fluoride are reacted to fluorinate 1220za. By the fluorination, 1,1-dichloro-1,3,3,3-tetrafluoropropane (234fb) is produced. In the fluorination, the amount of hydrogen fluoride used is preferably 4 to 40 mol, particularly preferably 8 to 40 mol, per 1220 za 1 mol. The fluorination is carried out at 0.1 to 10 MPaG, preferably 1.5 to 6 MaG, particularly preferably 3 to 6 MPaG. The fluorination is carried out in the presence or absence of a catalyst, preferably in the absence of a catalyst. The fluorination is performed in the presence or absence of a solvent, preferably in the absence of a solvent. Further, the fluorination may be carried out by a batch type, semi-continuous flow type or continuous flow type, and preferably by a continuous flow type. The fluorination is preferably performed in a liquid phase. The fluorination is preferably carried out at 20 to 200 ° C., more preferably 70 to 200 ° C., particularly preferably 100 to 200 ° C., further preferably 140 to 200 ° C. In addition, the fluorination produces 1,1-dichloro-3,3,3-trifluoropropene (1223za), 1,1,3-trichloro-3,3-difluoropropene (1222za) and the like together with 234fb. Sometimes. Moreover, it is preferable to refine | purify 234fb obtained by the said fluorination. Further, the produced 1222za or 1223za can be separated and used for various applications, respectively, and can also be used for fluorination together with 1220za.

In a preferred embodiment of the present invention, 1,1,3,3,3-pentachloropropene (1220za) and hydrogen fluoride are reacted to fluorinate 1220za. By the fluorination, 1,1-dichloro-3,3,3-trifluoropropene (1223za) and 1,1-dichloro-1,3,3,3-tetrafluoropropane (234fb) are produced together. In the fluorination, the amount of hydrogen fluoride used is 3 to 40 moles, preferably 4 to 40 moles, and particularly preferably 8 to 40 moles per mole of 1220za. The fluorination is performed at 0.1 to 10 MPaG, preferably 1.5 to 6 MaG, and particularly preferably 2.0 to 4.5 MPaG. The fluorination is carried out in the presence or absence of a catalyst, preferably in the absence of a catalyst. The fluorination is performed in the presence or absence of a solvent, preferably in the absence of a solvent. Further, the fluorination may be carried out by a batch type, semi-continuous flow type or continuous flow type, and preferably by a continuous flow type. The fluorination is preferably performed in a liquid phase. The fluorination is preferably carried out at 20 to 200 ° C., more preferably 70 to 200 ° C., particularly preferably 100 to 200 ° C., further preferably 140 to 200 ° C. The fluorination may produce 1,1,3-trichloro-3,3-difluoropropene (1222za) together with 1223za and 234fb. Moreover, it is preferable to refine | purify 1223za and 234fb obtained by the said fluorination. The co-produced 1223za and 234fb can be used for various purposes. Moreover, 1222za produced | generated can also be used for fluorination with 1220za.

In a preferred embodiment of the present invention, 1,1,3,3,3-pentachloropropene (1220za) is 1,1,1,3,3,3-hexachloropropane (CCl ₃ CH ₂ CCl ₃ ; hereinafter referred to as 230fa). (Also referred to as dehydrochlorination). The dehydrochlorination is preferably performed in the liquid phase. The dehydrochlorination is preferably performed in the presence of a Lewis acid catalyst, and particularly preferably performed in the presence of a Lewis acid catalyst in the liquid phase. The Lewis acid catalyst is preferably a metal halide, such as aluminum, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, tin, antimony, tantalum and tungsten. More preferred are halides of at least one metal selected from the group consisting of: chlorides of such metals are particularly preferred, chlorides of at least one metal selected from the group consisting of aluminum, iron, tin and antimony Is more preferable. In addition, the Lewis acid catalyst may be subjected to chlorination treatment of metal for the dehydrochlorination, aluminum, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, ruthenium. A material obtained by chlorinating at least one metal selected from the group consisting of rhodium, palladium, silver, tin, antimony, tantalum and tungsten. The dehydrochlorination is preferably performed at 40 to 200 ° C, more preferably 45 to 120 ° C.

In a preferred embodiment of the present invention, 1,1,3,3,3-pentachloropropene (1220za) is 1,1,1,3,3-pentachloropropane (CCl ₃ CH ₂ CHCl ₂ ; hereinafter also referred to as 240fa). ) To produce 1,1,1,3,3,3-hexachloropropane (230fa), which is produced by dehydrochlorination of 230fa. The chlorination is preferably performed by contacting 240fa with a chlorinating agent, and more preferably the chlorinating agent is chlorine. The contact is preferably performed in the presence of a radical initiator or under UV irradiation. The chlorination is preferably carried out at 0 to 150 ° C., more preferably 40 to 80 ° C. Further, 230fa obtained by the chlorination is preferably subjected to the dehydrochlorination without purification, more preferably the chlorination and the dehydrochlorination are successively performed, It is particularly preferred that the dehydrochlorination is carried out in the same reactor.

In this specification, “co-production of 1,1-dichloro-3,3,3-trifluoropropene (1223za) and 1,1,3-trichloro-3,3-difluoropropene (1222za)” This means that at least 1223za and 1222za are produced by the reaction according to the present invention, and preferably 1222za is produced by 0.0001 mol or more, particularly preferably 0.001 mol or more, per mol of 1223za.

In the present specification, “co-production of 1,1-dichloro-3,3,3-trifluoropropene (1223za) and 1,1-dichloro-1,3,3,3-tetrafluoropropane (234fb)” Means that at least 1223za and 234fb are produced by the reaction according to the present invention, and preferably 234fb is produced in an amount of 0.0001 mol or more, particularly preferably 0.001 mol or more, per mol of 1223za.

According to the present invention, it is possible to provide an efficient (easily industrially adopted) production method of 1223za using 1220za as a raw material and hydrogen fluoride as a fluorinating agent.

Further, according to the present invention, it is possible to provide an efficient co-production method of 1223za and 1222za and an efficient production method of 1222za.

Furthermore, according to the present invention, it is possible to provide an efficient production method of 1223za and 234fb and an efficient production method of 234fb.

Hereinafter, the present invention will be described. The present invention is not limited to the following embodiments, and appropriate modifications and improvements are made to the following embodiments based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Are also included in the present invention.

<Fluorination of 1,1,3,3,3-pentachloropropene (1220za)>
In one embodiment of the present invention, 1220za is fluorinated to produce 1,1-dichloro-3,3,3-trifluoropropene (1223za). This fluorination uses hydrogen fluoride as a fluorinating agent. This fluorination is carried out in the liquid phase or in the gas phase.

In the present invention, 1220za used as a raw material is a known compound. An example of the manufacturing method will be described later, but this does not prevent other manufacturing methods from being adopted. However, since 1220za can be advantageously manufactured by adopting the manufacturing method described later, it is preferable to employ this method.

In the fluorination of 1220za, the amount of hydrogen fluoride used is usually 3 to 40 moles, preferably 4 to 35 moles, more preferably 8 to 30 moles per mole of 1220za. The amount of hydrogen fluoride used is expressed with respect to the charged amount of 1220 za when the reaction type is a batch type or semi-continuous flow type, and in the case of the continuous flow type, the steady amount of 1220 za present in the reactor. Expressed against quantity. When the amount of hydrogen fluoride is less than 3 mol, the theoretical amount of hydrogen fluoride necessary to produce 1223za is not reached, and both the selectivity of the reaction and the yield of the target product may decrease. On the other hand, when the amount of hydrogen fluoride exceeds 40 mol, the amount of hydrogen fluoride not involved in the reaction increases, which is not economically preferable from the viewpoint of productivity. However, these do not preclude the use of less than 3 moles and more than 40 moles of hydrogen fluoride per mole of 1220za.

When fluorination of 1220za is carried out in the liquid phase and it is desired to produce 1222za predominantly, the amount of hydrogen fluoride used is preferably 2 to 40 mol, more preferably 3 to 35 mol. ˜30 mol is particularly preferred. Further, when the fluorination of 1220za is carried out in the liquid phase and it is desired to produce 234fb predominantly, the amount of hydrogen fluoride used is preferably 4 to 40 mol, more preferably 8 to 40 mol. .

In the fluorination of 1220za, it is preferable from the viewpoint of industrial production that unreacted hydrogen fluoride is separated from the reaction product and recycled to the reaction system. Separation of hydrogen fluoride and the reaction product can be performed by a known method, and examples of such a method include a method of distilling the reaction product.

In the fluorination of 1220za, the reaction temperature is not particularly limited as long as the target product can be produced.

When the fluorination of 1220za is carried out in the liquid phase, the reaction temperature is usually set in the range of 0 to 200 ° C, preferably 20 to 200 ° C, but is not limited thereto. In one embodiment of the present invention, the reaction temperature is preferably adjusted according to a desired object. For example, when it is desired to produce 1223za predominantly, 20 to 140 ° C. is preferable, and 20 to 130 ° C. is particularly preferable. In the case where 1223za and 1222za are co-produced, 0 to 70 ° C. is preferable, 0 to 60 ° C. is particularly preferable, and 10 to 55 ° C. is more preferable. When it is desired to produce 1222za predominantly, 0 to 70 ° C. is preferable, 0 to 60 ° C. is particularly preferable, and 10 to 55 ° C. is more preferable. In the case where 1223za and 234fb are produced together, the temperature is preferably 20 to 200 ° C, more preferably 70 to 200 ° C, particularly preferably 100 to 200 ° C, and further preferably 140 to 200 ° C. Further, when it is desired to produce 234fb predominantly, it is preferably 20 to 200 ° C, more preferably 70 to 200 ° C, particularly preferably 100 to 200 ° C, and further preferably 140 to 200 ° C.

When the fluorination of 1220za is carried out in the gas phase, the reaction temperature is usually set in the range of 100 to 500 ° C, preferably 150 to 400 ° C, particularly preferably 200 to 350 ° C, but is not limited thereto. In one embodiment of the present invention, the reaction temperature is preferably adjusted according to a desired object.

In the fluorination of 1220za, the pressure is not limited, and may be any of reduced pressure, normal pressure (atmospheric pressure), and increased pressure. In one embodiment of the present invention, the reaction pressure is usually 0.1 to 10 MPaG (referred to as gauge pressure, hereinafter the same), preferably 1.5 to 6 MPaG, more preferably 2.0 to 4.5 MPaG. If it is 0.1 MPaG or more, it can be easily raised to a suitable reaction temperature, and if it is 10 MPaG or less, the economic cost associated with the pressure resistance design of the reactor can be relatively low. However, these do not prevent the reaction from being performed at a pressure lower than 0.1 MPaG or higher than 10 MPaG.

When the fluorination of 1220za is carried out in the liquid phase, the fluorination of 1220za may be carried out in the presence of a salt composed of an organic base such as an amine compound, an amide compound, a sulfonyl compound, or a phosphorus compound and hydrogen fluoride. Examples include triethylamine, diisopropylamine, tri-n-butylamine, pyridine, 2,6-lutidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, DMAC, DMF, DMSO, triphenylphosphine, and the like. However, it is not limited to these.

Fluorination of 1220za may be performed in the presence or absence of a catalyst.

When fluorination of 1220za is carried out in the presence of a catalyst in the liquid phase, the catalyst includes alkali metals, alkaline earth metals, transition metals, base metals, metalloids, simple substances, derivatives, or two or more of these Use a mixture. More specifically, zero-valent metals, hydroxides, oxides, halides, organic or inorganic salts, and complexes selected from alkali metals, alkaline earth metals, transition metals, base metals, and semimetals. More specifically, chlorides, fluorides and the like selected from tin, titanium, antimony, aluminum, and iron are exemplified, but not limited thereto.

When performing fluorination of 1220za in the gas phase in the presence of a catalyst, a metal catalyst is used as the catalyst. Specifically, the metal catalyst is aluminum, vanadium, chromium, titanium, magnesium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, tin, antimony, zinc, It contains at least one metal selected from the group consisting of lanthanum, tantalum and tungsten, and compounds of such metals are preferred, and oxides, halides and oxyhalides of such metals are more preferred (where halogens Are specifically iodine, bromine, chlorine, and fluorine. The metal catalyst is more preferably a partial halide or total halide of such a metal, particularly preferably a partial fluoride or total fluoride of such a metal.

The metal catalyst may be a supported catalyst or a non-supported catalyst. The carrier in the case of the supported catalyst is not particularly limited, but it is preferable to employ carbon, the above-mentioned metal oxides, oxyhalides (preferably oxyfluorides), halides (preferably fluorides) and the like. Among such carriers, particularly preferably, activated carbon or an oxide of at least one metal selected from the group consisting of aluminum, chromium, zirconium and titanium, an oxyhalide (particularly preferably an oxyfluoride), a halide (particularly, Preferred is fluoride). The supported material in the case of the supported catalyst is a compound of the above-mentioned metal, for example, as the above-mentioned metal fluoride, chloride, fluorinated chloride, oxyfluoride, oxychloride, oxyfluorinated chloride, glass oxide, etc. Supported on a carrier. Such metal compounds may be supported alone or in combination of two or more. In one embodiment of the present invention, the supported product in the case of a supported catalyst is chromium nitrate, chromium trichloride, potassium dichromate, titanium trichloride, manganese nitrate, manganese chloride, ferric chloride, nickel nitrate, nickel chloride, nitric acid. Cobalt, cobalt chloride, antimony pentachloride, magnesium chloride, magnesium nitrate, zirconium chloride, zirconium oxychloride, zirconium nitrate, copper (II) chloride, zinc (II) chloride, lanthanum nitrate, tin tetrachloride and the like are used.

In one embodiment of the present invention, the metal catalyst is preferably subjected to a fluorination treatment for use in use. The method of this fluorination treatment is not particularly limited, but is generally carried out by bringing the metal catalyst into contact with a fluorinating agent such as hydrogen fluoride, fluorinated hydrocarbon, or fluorinated chlorinated hydrocarbon. Although the fluorination treatment temperature is not particularly limited, it is usually carried out at 200 ° C. or higher, and there is no particular upper limit on the temperature, but practically it is preferably carried out at 600 ° C. or lower.

Fluorination of 1220za may be performed in the presence or absence of a filler. Examples of the material for the filler include carbon such as activated carbon, and metals such as heat-resistant plastic, ceramics, and stainless steel. Among these, activated carbon is particularly preferable.

Usually, in the case of a gas-phase flow reaction, productivity is often discussed in terms of the value (seconds) obtained by dividing the reaction zone volume A (mL) by the raw material supply rate B (mL / second). Call time. When the catalyst and / or filler is provided in the reaction zone, the apparent volume (mL) of the catalyst and / or filler is regarded as A above. The value of B indicates “volume of the raw material gas introduced into the reactor per second”. In this case, the raw material gas is regarded as an ideal gas, and the value of B is determined from the number of moles, pressure and temperature of the raw material gas. Is calculated. In the reactor, by-products of other compounds than the raw material and the target product and a change in the number of moles may occur, but they are not taken into account when calculating the “contact time”.

The determination of the optimum contact time depends on the reaction raw material, reaction temperature, catalyst, type of filler, etc. used in the method of the present invention. For this reason, it is desirable to optimize the contact time by appropriately adjusting the supply rate of the reaction raw material for each reaction raw material, the set temperature of the reaction apparatus, and the type of catalyst.

When fluorination of 1220za is carried out in the gas phase in the presence of a catalyst, the contact time is usually 0.1 to 300 seconds, preferably 5 to 150 seconds, more preferably 10 to 100 seconds. It is not limited and may be changed as appropriate.

In the fluorination of 1220za, it is preferable not to use a solvent from the viewpoint of productivity and economy. On the other hand, a solvent can be used in consideration of the uniformity of the reaction and the operability after the reaction. The kind of the solvent to be used is not particularly limited as long as the raw material 1220za can be dissolved. Among them, an organic compound having a boiling point higher than 1223za and not fluorinated by hydrogen fluoride during the reaction is preferable. Examples of such solvents include, but are not limited to, tetramethylene sulfone (sulfolane), perfluoroalkanes, perfluoroalkenes, hydrofluorocarbons, and the like. Further, the amount of the solvent to be used is not particularly limited as long as the raw material 1220za can be dissolved. 80 mass% or less is preferable with respect to 1220za, and 40 mass% or less is more preferable.

Fluorination of 1220za may be performed by any of batch, semi-continuous flow, and continuous flow methods. The reactor is preferably a liquid phase reactor or a gas phase reactor depending on the reaction. Examples of the material for the reactor include, but are not limited to, stainless steel (for example, SUS304 and SUS316), Hastelloy (TM), Inconel (TM), Monel (TM), and the like. Such reactors are well known in the art.

The procedure for fluorination of 1220za is not particularly limited. An example is shown below. In batch-type operation and semi-continuous flow-type operation, for example, when a predetermined amount of a predetermined raw material is introduced into a reactor and the fluorination is performed by a liquid phase reaction, a predetermined amount of a solvent is introduced as desired. The procedure etc. which perform reaction by are illustrated. When using a catalyst, it is preferable to introduce the catalyst into the reactor in advance or together with the raw materials and the solvent. Moreover, the introduction procedure of the raw material to a reactor is not specifically limited. For example, 1220za may be introduced into the reactor and then hydrogen fluoride may be introduced into the reactor. At this time, when a solvent is introduced as desired, a part or all of the solvent may be introduced into the reactor before introducing hydrogen fluoride into the reactor, or separately with the introduction flow of hydrogen fluoride. The solvent may be introduced into the reactor in a stream or in a stream with hydrogen fluoride.

In continuous flow operation, for example, a reactor is introduced with a predetermined amount of 1,1,3,3,3-pentachloropropene (1220za) and hydrogen fluoride in separate flows, and 1220za under predetermined conditions. The procedure etc. which perform fluorination of are illustrated. When the fluorination is performed in a liquid phase reaction, a solvent used as desired may be introduced into the reactor separately from 1220za and hydrogen fluoride, or as a 1220za solution or a hydrogen fluoride solution.

The method for purifying 1223za from the reaction product obtained by fluorination of 1220za is not particularly limited, and a known purification method can be employed. If necessary, the chlorine product and the acid component that may be contained in the reaction product may be removed by a method such as washing the reaction product with water. In addition, water in the reaction product may be removed by performing a dehydration treatment or the like, and this may be performed in combination with a removal treatment of a chlorine component or an acid component. Moreover, you may perform operation, such as distillation. Although an example of the purification method of 1223za is shown below, it is not limited to this. For example, the reaction product is passed through a cooled condenser to be condensed, washed with water or / and alkaline solution to remove chlorine component, acid component, etc., dried with a desiccant such as zeolite, activated carbon, etc. By the distillation operation, 1223za with high purity can be obtained.

Fluorination of 1220za may produce by-products such as 1221za, 1222za, 234fb, 235fa, and 236fa. When the unreacted raw material 1220za is present in the reaction product, or when these by-products are present, these compounds can be separated from the reaction product and recovered by ordinary distillation operations. Depending on the separated 1220za and the types of these by-products (for example, underfluorinated compounds such as 1221za and 1222za), they can be reused as a raw material for the reaction according to the present invention. These compounds may be used for various applications as they are.

Also, underfluorinated compounds such as 1221za and 1222za can be converted to 1223za by further fluorination. Therefore, such underfluorinated products may be used as a reaction raw material in the reaction system in the same manner as 1220za. Thereby, 1223za can be manufactured efficiently. Further, such a small fluorinated product may be taken out from the reaction product and fluorinated separately.

In the reaction according to the present invention, the obtained 1,1-dichloro-3,3,3-trifluoropropene (1223za) exists as a liquid at normal temperature and normal pressure.

<Method for producing 1,1,3,3,3-pentachloropropene (1220za)>
An example of a manufacturing method of 1220za is shown below. By producing 1220za by this method and using this 1220za as a raw material for the reaction according to the present invention, 1,1,1,3,3,3-hexachloropropane (230fa) described later or 1,1,1,3 1,3-pentachloropropane (240fa) can be used as a starting material to produce 1223za efficiently.

1220za can be produced by a process including at least a step of dehydrochlorinating 230fa in the liquid phase in the presence of a Lewis acid catalyst (hereinafter sometimes referred to as “dehydrochlorination step”). it can.

Furthermore, 230fa can be manufactured by a method including at least a step of chlorinating 240fa (hereinafter, sometimes referred to as “chlorination step”), and it is preferable to do so. This does not preclude the use of 230fa produced by other methods in the dehydrochlorination step.

“Moisture” is described as common to both chlorination and dehydrochlorination processes. In both the reactions of the chlorination step and the dehydrochlorination step, water does not actively participate in the reaction. Therefore, in the present invention, there is no positive reason for adding water to the reaction system. In particular, when the reaction is carried out in the presence of a Lewis acid catalyst, it is preferable to carry out the reaction under conditions where “moisture” is as low as possible (generally referred to as anhydrous conditions) in order to increase the activity of the Lewis acid. However, the activity of the Lewis acid is sufficiently maintained as long as 1% by mass of water is present with respect to the total mass of the reaction solution. Therefore, the water content is desirably maintained at 1% by mass or less, more preferably 0.1% by mass or less, with respect to the total mass of the reaction solution.

Also, no solvent is required for any reaction in the chlorination step or the dehydrochlorination step. When these reactions are performed in a liquid phase reaction, the raw materials / products 240fa, 1230za, 230fa, and 1220za all form a stable liquid phase by themselves, and in the liquid phase mainly composed of these, The intended reaction proceeds. Note that this does not prevent the reaction of either the chlorination step or the dehydrochlorination step from being carried out in the presence of a solvent, but when a solvent is used, these reactions are not adversely affected. It is preferable to employ one capable of performing a liquid phase reaction.

Furthermore, as common to both reactions of the chlorination step and the dehydrochlorination step, it is not essential to perform these steps in the presence of an inert gas (nitrogen gas, argon gas, etc.). However, when the reaction is performed while flowing nitrogen gas, a smoother reaction may be performed particularly when the reaction is performed on a large scale. Such an optimal reaction embodiment can be appropriately set according to the knowledge of those skilled in the art.

Hereinafter, the chlorination process and the dehydrochlorination process will be described for each process.

1. Chlorination process The chlorination process is a process in which 1,1,1,3,3-pentachloropropane (240fa) is chlorinated to obtain 1,1,1,3,3,3-hexachloropropane (230fa). .

240fa is a starting material of 1,1,1,3,3-pentafluoropropane (245fa) that is currently industrially produced as a blowing agent, and reacts carbon tetrachloride and vinyl chloride in the presence of a catalyst. (See, for example, US Pat. No. 7,094,936).

In one embodiment of the present invention, chlorination of 240fa is performed by contacting 240fa with a chlorinating agent (preferably chlorine). This contact may be in any form, for example, contact by introducing 240fa into a reactor into which a chlorinating agent has been previously introduced, or introducing the chlorinating agent and 240fa into the reactor in separate flows. Examples of such contact include, but are not limited to, contact by introducing a chlorinating agent into a reactor into which 240 fa has been introduced in advance. Especially, the contact by blowing in and introducing a gaseous chlorinating agent (for example, chlorine gas) with respect to 240fa of a liquid state is suitable. In one embodiment of the present invention, this reaction is preferably performed in the presence of a radical initiator or under UV irradiation, and particularly preferably performed in the presence of a radical initiator and under UV irradiation, from the viewpoint of reaction efficiency. In another embodiment of the present invention, this reaction is performed under UV irradiation without using a radical initiator because it shows good acceleration of the chlorination reaction and easy purification after the reaction. It is preferable.

In the chlorination step, the chlorinating agent used is not particularly limited. In one embodiment of the present invention, the chlorinating agent is not particularly limited as long as it generates chlorine (chlorine radical). For example, chlorine, sulfuryl chloride, N-chlorosuccinimide and the like can be mentioned, among which chlorine is preferable.

In the chlorination step, the amount of chlorinating agent used is not particularly limited as long as 230fa is produced. A chlorinating agent is usually used in an amount of 0.3 to 1.5 equivalents, preferably 0.5 to 1 equivalent, relative to 240fa.

In the chlorination step, examples of the radical initiator used include azo compounds, organic peroxides, triethylborane, and diethylzinc. In addition, a zero-valent metal complex or the like may be used. Such radical initiators may be used alone or in combination. Examples of the azo compound include, but are not limited to, azobisisobutyronitrile (AIBN), 1,1'-azobis (cyclohexanecarbonitrile) (ABCN), and the like. Examples of the organic peroxide include, but are not limited to, tert-butyl hydroperoxide (TBHP) and benzoyl peroxide (BPO).

In the chlorination step, the amount of radical initiator used is not particularly limited as long as it is an effective amount. In one embodiment of the present invention, the amount of the radical initiator used is 0.01 to 1% by mass, preferably 0.1 to 0.3% by mass with respect to 240fa.

The reaction temperature in the chlorination step is not particularly limited. In one embodiment of the present invention, the reaction temperature in the chlorination step is preferably about 0 to 150 ° C., and particularly preferably 40 to 80 ° C. from the viewpoint of reaction efficiency.

The reaction time in the chlorination process is not particularly limited. In the chlorination step, 240fa in the liquid phase inside the reactor is replaced with 230fa, which is the object, over time. It is preferable to adjust so that the highest selectivity to 230fa is achieved while confirming the progress of the reaction by gas chromatographic analysis or the like of the sampled reactant. In one embodiment of the present invention, the reaction is preferably terminated when about 240 to 80% of the raw material is consumed, more preferably about 40 to 70%, and particularly preferably about 50 to 60%. Absent. Thereby, the byproduct of the compound in which 230fa is further chlorinated can be suppressed. This does not prevent the reaction from being terminated when less than 30% of the raw material 240fa is consumed or when more than 80% is consumed.

In the chlorination step, 1,1,1,2,3,3-hexachloropropane (hereinafter also referred to as 230da) may be generated by the chlorination reaction. 230da is a kind of 240fa chlorinated derivative, and 1220za can be produced by dehydrochlorination of 230da. Therefore, in the dehydrochlorination step, pure 230fa may be used as a feedstock, or a mixture of 230fa and 230da may be used. Further, 230da may be used in place of 230fa as a feedstock for the dehydrochlorination step.

230fa obtained in the chlorination step can be purified by a general purification operation. For example, the raw material 240fa can be easily separated from 230fa by an operation such as distillation, preferably vacuum distillation. The separated 240fa can be reused as a raw material for the chlorination process.

In addition, 230fa synthesized by the chlorination step can be used as a raw material for the subsequent dehydrochlorination step without performing post-treatment such as catalyst separation and distillation purification. This does not prevent the post-treatment, but one of the great advantages of the present invention is that the chlorination step and the dehydrochlorination step can be carried out continuously without performing the post-treatment. As such, it is a preferred embodiment that no such post-processing is performed.

In the chlorination process, the material of the reactor (reactor) is not particularly limited. When a highly oxidizing chlorinating agent (for example, chlorine gas) is used, those made of glass or stainless steel are preferred. A reactor lined with glass or resin is also preferred. The reactor is preferably equipped with various facilities such as a blowing tube, a stirring facility, a reflux tower and the like.

2. Dehydrochlorination Step The dehydrochlorination step is a step of obtaining 1220za by dehydrochlorinating 230fa in the presence of a Lewis acid catalyst in the liquid phase.

In the dehydrochlorination step, the material of the reactor (reactor) is not particularly limited. Since it is a reaction in which hydrogen chloride is generated, a material having acid resistance is preferable. Specifically, a material made of glass or stainless steel, a material lined with glass or resin, or the like can be given. Furthermore, the reactor is preferably equipped with various facilities such as a stirring facility and a reflux tower. In the case where the chlorination step and the dehydrochlorination step are performed in the same reactor, when a gaseous chlorinating agent (for example, chlorine) is used, it is preferable to include a blowing tube into which the chlorinating agent can be introduced. In the case of the reaction “in the liquid phase and in the presence of a Lewis acid catalyst”, the reaction proceeds sufficiently at a reaction temperature of 200 ° C. or lower as described later. This is not necessarily higher than the boiling point of 230fa or 1220za, so if a reflux tower is provided, the reaction mixture can be kept in a liquid state at normal pressure, so that the reaction is carried out at normal pressure (open system). be able to. This does not preclude the adoption of a method in which the reaction is performed using a pressure reactor and the generated hydrogen chloride is purged in a timely manner.

Examples of the Lewis acid catalyst used in the dehydrochlorination step include metal halides. The metal halide refers to one having a bond between a metal atom and a halogen atom. If the bond between the metal atom and the halogen atom is confirmed by infrared spectroscopy (IR method), X-ray diffraction method (XRD method), X-ray photoelectron spectroscopy (XPS method), etc., it can be used as the catalyst of the present invention. . Specifically, at least one selected from the group consisting of aluminum, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, tin, antimony, tantalum and tungsten. Certain metal halides are preferred. Such metal halides may be fluorides, chlorides, bromides, and iodides. Of these, chlorides are preferred. More specifically, at least one metal chloride selected from the group consisting of aluminum, iron, tin and antimony is particularly preferred. Among these, aluminum chloride and iron chloride are more preferable, and in the case of iron chloride, ferric chloride is preferable. An anhydrous Lewis acid catalyst is preferable because of its high catalytic activity. Commercially available anhydrides may be used as they are, or hydrates may be treated with a dehydrating agent such as thionyl chloride to obtain anhydrides.

When the above-mentioned metal chloride is used as the Lewis acid catalyst, the metal nitrate, carbonate, etc. or zero-valent metal powder can be derived into the above-mentioned metal chloride by treating with hydrogen chloride in advance. This can also be used as a Lewis acid catalyst. In addition, the above metal zero-valent metal powders, carbonates and nitrates are produced by hydrogen chloride by-produced by chlorination of 240fa in the chlorination process and hydrogen chloride generated by the dehydrochlorination reaction of 230fa in the dehydrochlorination process. Can be derived into the above-mentioned metal chloride, the Lewis acid catalyst used in the chlorination step or dehydrochlorination step may be a zero-valent metal powder, a metal carbonate, or a metal nitrate. .

The amount of the Lewis acid catalyst is not particularly limited as long as it is an effective amount as a catalyst. The optimum value varies depending on the operating conditions such as the type of catalyst and reaction temperature, but the reaction proceeds at a good reaction rate and unexpected side reactions are unlikely to occur. The content is 0.01 to 10 mol%, more preferably 0.1 to 5 mol% with respect to the organic matter.

When the reaction in the dehydrochlorination step is performed “in the liquid phase in the presence of a Lewis acid catalyst”, the reaction temperature is usually set in the range of 40 to 200 ° C., more preferably 45 to 120 ° C. The optimum temperature also depends somewhat on the type of Lewis acid catalyst. For example, when aluminum chloride is used as the Lewis acid catalyst, 40 to 100 ° C. (typically 50 to 80 ° C.) is particularly preferable, and when ferric chloride is used, 50 to 110 ° C. (typically higher than this) In particular, 60 to 80 ° C. is particularly preferable. Thereby, the reaction proceeds at a good reaction rate, and the production of by-products is also suppressed, so that 1220za can be obtained with a good selectivity.

As a preferred embodiment of the dehydrochlorination step, there is a method in which a Lewis acid catalyst and 230fa are charged into a reactor equipped with a reflux tower, and the inside of the reactor is heated while stirring. Thereby, only hydrogen chloride can be discharged out of the reactor from the reflux tower through which water (tap water, industrial water, etc.) is circulated. Although this reactor is not specifically limited, It is preferable to be comprised from the material resistant to reaction, for example, the reactor made from glass and the reactor made from glass lining are used.

The reaction time in the dehydrochlorination step is not particularly limited. In the dehydrochlorination step, the liquid phase inside the reactor is replaced with the target 1220za as time passes. It is preferable to terminate the reaction when 230fa is almost consumed while confirming the progress of the reaction by gas chromatographic analysis or the like of the sampled reactant.

The reaction in the dehydrochlorination step can be carried out in the gas phase and without a catalyst. In the case of this gas phase non-catalytic reaction, the reaction temperature is usually 200 to 550 ° C., and the load on the apparatus is generally large due to the high temperature. May be advantageous.

1220za obtained by the dehydrochlorination step can be used as a raw material for the subsequent fluorination reaction of 1220za without performing post-treatment such as separation of the catalyst and purification by distillation. This does not prevent the post-treatment such as separation of the catalyst and purification by distillation. However, one of the great advantages of the present invention is that each step can be carried out continuously without performing the post-treatment. Therefore, it is a preferable aspect not to perform such post-processing.

The present invention will be described with reference to the following examples, but the present invention is not limited to the following examples.

In this specification, FID% refers to the area% when the detector analyzes by FID gas chromatograph. In the text, the simple purity conversion yield of 1223za, the simple purity conversion yield of 1222za, and the simple purity conversion yield of 234fb are respectively calculated according to the following formulas.
Simple purity conversion yield of 1223za = 100 × (recovered organic matter amount × 1223zaFID% / 1223za molecular weight) / (1220za charge amount × 1220za purity / 1220za molecular weight)
Simple purity conversion yield of 1222za = 100 × (recovered organic matter amount × 1222zaFID% / 1222za molecular weight) / (1220za charge amount × 1220za purity / 1220za molecular weight)
Simple purity conversion yield of 234fb = 100 × (recovered organic matter amount × 234fbFID% / 234fb molecular weight) / (1220za charge amount × 1220za purity / 1220za molecular weight)

(A) Fluorination of 1220za (A-1) Liquid phase fluorination of 1220za [Example 1-1]
30 g of 1,1,3,3,3-pentachloropropene (1220za) with a purity of 94.7% was added to a 300 mL stainless steel autoclave equipped with a condenser and a pressure gauge in which a coolant at 20 ° C. was circulated. 0.131 mol) and 26.0 g of hydrogen fluoride (1.30 mol, 12.20 za / hydrogen fluoride molar ratio = about 1/10) were introduced, and then the autoclave was heated to 120 ° C. When the pressure exceeded about 4 MPaG, the reaction product gas was extracted from the needle valve at the condenser outlet so as to maintain 4.0 to 4.5 MPaG. The extracted gas was passed through a fluororesin gas washing bottle containing ice water cooled in an ice water bath to absorb the acid, and the reaction product organic matter was recovered with a glass trap of a dry ice acetone bath. Three hours after the start of temperature increase, after confirming that the pressure increase was no longer observed, the reactor was purged, and the extracted gas was a fluororesin gas cleaning bottle containing ice water cooled in an ice water bath and dry ice. It collected in the glass trap of the acetone bath. After cooling the reactor, the reaction liquid in the autoclave and the glass trap collection from the dry ice acetone bath are all mixed in a fluororesin gas washing bottle containing ice water, and the combined solution is mixed with organic substances in a fluororesin separatory funnel. Was separated from the aqueous phase and recovered. The amount of the collected organic matter was 20.3 g.

[Example 1-2]
The reaction was carried out in the same manner as in Example 1-1 except that the reaction temperature was 80 ° C. Since the maximum pressure was 3.5 MPaG, no gas was extracted. The amount of recovered organic matter was 17.8 g.

[Example 1-3]
The reaction was performed in the same manner as in Example 1-1 except that the reaction temperature was 50 ° C. Since the maximum pressure was 2.5 MPaG, no gas was extracted. The amount of recovered organic matter was 18.6 g.

[Example 1-4]
The reaction was carried out in the same manner as in Example 1-1 except that the reaction temperature was 30 ° C., the reaction pressure was normal pressure, and the reaction time was 5 hours. The amount of recovered organic matter was 24.8 g.

[Example 1-5]
10 g (0.044 mol) of 1,1,3,3,3-pentachloropropene (1220za) having a reaction temperature of 160 ° C. and a purity of 94.7%, 27.0 g (1.35 mol, 12.20 mol) of hydrogen fluoride The reaction was carried out in the same manner as in Example 1-1 except that the hydrogen / hydrogen fluoride molar ratio was about 1/30). The amount of the collected organic matter was 7.1 g.

[Example 1-6]
The outside of a 1000 mL stainless steel autoclave equipped with a condenser and a pressure gauge in which a coolant at 20 ° C. was circulated was cooled with an ice-water bath, and 1,1,3,3,3- After introducing 500 g (2.2 mol) of pentachloropropene (1220za) and 220.0 g of hydrogen fluoride (11.0 mol, 12.20 za / hydrogen fluoride molar ratio = about 1/5), the autoclave was heated to 50 ° C. Heated. When the pressure exceeded about 0.2 MPaG, the reaction product gas was extracted from the needle valve at the condenser outlet so as to maintain 0.20 to 0.25 MPaG. The extracted gas was passed through a fluororesin gas washing bottle containing ice water cooled in an ice water bath to absorb the acid, and the reaction product organic matter was recovered with a glass trap of a dry ice acetone bath. After confirming that no pressure increase was observed 5 hours after the start of temperature increase, the reactor was purged, and the extracted gas was a fluororesin gas cleaning bottle containing ice water cooled in an ice water bath and dry ice. It collected in the glass trap of the acetone bath. After cooling the reactor, the reaction liquid in the autoclave and the glass trap collection from the dry ice acetone bath are all mixed in a fluororesin gas washing bottle containing ice water, and the combined solution is mixed with organic substances in a fluororesin separatory funnel. Was separated from the aqueous phase and recovered. The amount of the collected organic matter was 432 g.

[Example 1-7]
After introducing 440.0 g of hydrogen fluoride (22.0 mol, 1220 za / hydrogen fluoride molar ratio = about 1/10), the autoclave was heated, and when the pressure exceeded about 0.3 MPaG, 0.30-0 The reaction was carried out in the same manner as in Example 1-6, except that the reaction product gas was extracted from the needle valve at the outlet of the condenser so as to maintain 35 MPaG. The amount of organic matter recovered was 350 g.

[Example 1-8]
An autoclave charged with 500 g of 1,1,3,3,3-pentachloropropene (1220za) and heated to 50 ° C. had 440.0 g of hydrogen fluoride (22.0 mol, 1220 za / hydrogen fluoride molar ratio = about 1). / 10) is introduced over 4 hours, and the reaction product gas is extracted from the needle valve at the outlet of the condenser so as to maintain 0.30 to 0.35 MPaG when the pressure exceeds about 0.3 MPaG. The reaction was carried out in the same manner as 1-6. The amount of the collected organic matter was 343 g.

Table 1 shows a summary of the reaction conditions (1220za / hydrogen fluoride molar ratio, reaction temperature, reaction pressure) for Examples 1-1 to 1-8. For Examples 1-1 to 1-8, the composition of the recovered organic substance was analyzed by gas chromatography, and the simple purity conversion yields of 1223za, 1222za, and 234fb were calculated. These results are shown in Table 2. In Table 2, “-” indicates that no detection was made.

[Example 2]
A glass distillation column equipped with an electromagnetic reflux apparatus, a reflux timer, and a 2 L three-neck flask was filled with 20 stages of Helipac NO2. Next, the recovered organic substances obtained in Examples 1-6 to 1-8 were mixed, and 1100 g of the collected organic substances were charged and distilled. 450 g of a fraction having a tower top temperature of 55.0 to 55.3 ° C. (1223za purity of 99.97 FID%) was recovered (corresponding to fraction 2 in Table 3). In addition, each fraction shown in Table 3 was obtained. In Table 3, “-” indicates that no detection was made.

[Example 3]
The fraction 4 separately collected in the distillation of Example 2 and the kettle residue were mixed and washed with water and dried using molecular sieves. The same reaction as in Example 1-7 was carried out using 500 g of the dried organic substance and 440 g of hydrogen fluoride. The amount of collected organic matter was 380 g.
The result of analyzing the composition of the collected organic matter by gas chromatography is shown below:
1,1-dichloro-3,3,3-trifluoropropene (1223za): 80.3 FID%;
1,1,3-trichloro-3,3-difluoropropene (1222za): 0.9FID%;
1,1-dichloro-1,3,3,3-tetrafluoropropane (234fb): 0.1 FID%;
Hexachloroethane (C2Cl6): 3.5FID%;
1-chloro-3,3,3-trifluoropropene (1233zd): 12.0FID%;
Other compounds: 3.2 FID%.
In addition, 1,1,3,3-tetrachloro-3-fluoropropene (1221za) and 1,1,3,3,3-pentachloropropene (1220za) were not detected.

(B) Preparation and fluorination of 1,1,3,3,3-pentachloropropene (1220za) [Example 4-1] 1,1,1,3,3-pentachloropropane under liquid phase and UV irradiation Chlorination of (240fa) 1,1,1,3,3-pentachloropropane (240fa) with a purity of 98.6FID% in a 3000 mL four-necked flask equipped with a ball filter, thermometer, Dimroth capable of running tap water and a stir bar 2000.0 g (9.4 mol) was charged and stirring was started. The top of the Dimroth was connected to a 500 mL-PFA container containing a 5 L-water trap and then 250 g of a 25 wt% potassium hydroxide aqueous solution using a PFA tube. Irradiation from a high-pressure UV lamp equipped with a water-cooling jacket over the glass from the upper outer side of the flask, the lower part of the flask was heated to 60 ° C. with a water bath, and 673 g (9.5 mol) of chlorine was introduced from a ball filter over 360 minutes. After introducing chlorine, the reactor was cooled to complete the reaction. The residue in the flask was washed with water and with a weak alkaline aqueous solution to recover 2326 g of organic matter.
The results of analyzing the collected organic matter by gas chromatography are shown below:
1,1,1,3,3,3-hexachloropropane (230fa): 49.3FID%;
1,1,1,2,3,3-hexachloropropane (230da): 9.8FID%;
1,1,1,3,3-pentachloropropane (240fa): 33.4FID%;
Two heptachloropropane isomers (220 isomers): 6.1 FID%;
Other compounds: 1.4 FID%.
A glass distillation tower equipped with an electromagnetic reflux apparatus, a reflux timer, a pressure reduction line, a pressure gauge, and a 2 L three-necked flask was filled with 10 stages of glass Raschig rings, and 2300 g of the recovered organic matter was charged. Each distillate shown in Table 4 and a kettle residue liquid 253g were obtained.

[Example 4-2]
In a 2000 mL three-necked flask equipped with a ball filter, thermometer, Dimroth capable of flowing tap water and a stirrer, 910 g of fraction 3 obtained in Example 4-1 and 0.93 g (0.006 mol) of ferric chloride were obtained. ) And stirring was started. At the top of the Dimroth, an empty trap of a 500 mL-PFA container was connected using a PFA tube, and then a 500 mL-PFA container containing 250 g of a 25 wt% sodium hydroxide aqueous solution. While introducing nitrogen from the ball filter at a flow rate of 30 mL / min, the flask was heated to 80 ° C. in an oil bath over 3 hours, and held for 1 hour, and the residual liquid in the kettle was sampled.
The results of analyzing the sampled kettle residue by gas chromatography are shown below:
1,1,1,3,3-pentachloropropane (240fa): 1.3FID%;
1,1,3,3-tetrachloropropene (1230za): 3.0FID%;
1,1,3,3,3-pentachloropropene (1220za): 83.8FID%;
1,1,1,3,3,3-hexachloropropane (230fa): 0.05 FID%;
1,1,1,2,3,3-hexachloropropane (230da): 10.5FID%;
Other compounds: 1.5 FID%.

[Example 4-3]
A glass distillation column equipped with an electromagnetic reflux apparatus, a reflux timer, a pressure reduction line, a pressure gauge, and a 1 L three-necked flask was filled with 10 stages of glass Raschig rings, and the recovered organic matter obtained in Example 4-1 was charged at a temperature of 74 500 g of a fraction having a pressure of ˜75.6 ° C. and a pressure of 2.0 KPaG was obtained.
The results of gas fraction analysis of this fraction are shown below:
1,1,1,3,3-pentachloropropane (240fa): 2.7 FID%;
1,1,3,3-tetrachloropropene (1230za): 0.1 FID%;
1,1,3,3,3-pentachloropropene (1220za): 94.7 FID%;
1,1,1,3,3,3-hexachloropropane (230fa): 0.1 FID%;
1,1,1,2,3,3-hexachloropropane (230da): 0.05 FID%;
Other compounds: 2.3 FID%.

[Example 4-4]
In a 2000 mL three-necked flask equipped with a ball filter, thermometer, Dimroth capable of flowing tap water and a stirrer, 250 g of fraction 4 obtained in Example 4-1, 0.31 g of ferric chloride (0.002 mol) ) And stirring was started. The same operation as in Example 4-2 was performed, except that the flask was heated to 120 ° C. in an oil bath for 3 hours.
The results of analyzing the sampled kettle residue by gas chromatography are shown below:
1,1,3,3-tetrachloropropene (1230za): 0.1 FID%;
1,1,3,3,3-pentachloropropene (1220za): 62.8FID%;
1,1,1,3,3,3-hexachloropropane (230fa): 0.01 FID%;
1,1,1,2,3,3-hexachloropropane (230da): 1.5FID%;
1,1,2,3,3-pentachloropropene (1220xa): 30.2FID%;
Two heptachloropropane isomers (220 isomers): 2.0 FID%;
Hexachloro-1,3-butadiene (C4Cl6): 1.0 FID%;
Other compounds: 2.5 FID%.
In addition, 1,1,1,3,3-pentachloropropane (240fa) was not detected.

[Example 5-1] Chlorination of 1,1,1,3,3-pentachloropropane (240fa) under liquid phase, UV irradiation 3000 mL equipped with a ball filter, thermometer, Dimroth capable of running tap water and stir bar In a four-necked flask, 1000.0 g (4.7 mol) of 1,1,1,3,3-pentachloropropane (240fa) having a purity of 98.6FID% and fractions 1 and 2 of Example 4-1 were charged and stirred. Started. The top of the Dimroth was connected to a 500 mL-PFA container containing a 5 L-water trap and then 250 g of a 25 wt% potassium hydroxide aqueous solution using a PFA tube. The flask was heated to 60 ° C. in an oil bath, and 600 g (0.8 mol) of chlorine was introduced from a ball filter over 300 minutes. After introducing chlorine, nitrogen was blown in at 100 mL / min for 100 minutes, and then the reactor was cooled to complete the reaction. After the reaction was completed, 2284 g of the residual liquid (organic matter) in the flask was recovered.
The results of gas chromatography analysis of the recovered kettle residue are shown below:
1,1,1,3,3,3-hexachloropropane (230fa): 50.9FID%;
1,1,1,2,3,3-hexachloropropane (230da): 9.5FID%;
1,1,1,3,3-pentachloropropane (240fa): 26.8FID%;
Two heptachloropropane isomers (220 isomers): 10.1 FID%;
Other compounds: 2.7% FID.

[Example 5-2]
In a 2000 mL three-necked flask equipped with a ball filter, a thermometer, a Dimroth capable of running tap water and a stirrer, 2284 g of the residue from the vessel (organic matter) obtained in Example 5-1, 3.0 g of ferric chloride (0. 02 mol) was charged, and the same operation as in Example 4-2 was performed. The results of gas chromatographic analysis after 4 hours of reaction are shown below:
1,1,1,3,3-pentachloropropane (240fa): 1.5 FID%;
1,1,3,3-tetrachloropropene (1230za): 25.7FID%;
1,1,3,3,3-pentachloropropene (1220za): 51.8FID%;
1,1,1,3,3,3-hexachloropropane (230fa): 0.2FID%;
1,1,1,2,3,3-hexachloropropane (230da): 9.5FID%;
Two heptachloropropane isomers (220 isomers): 9.2 FID%;
Other compounds: 2.1 FID%.

[Example 6] A liquid phase, a radical initiator, chlorination of 1,1,1,3,3-pentachloropropane (240fa) under UV irradiation, a ball filter, a thermometer, a Dimroth capable of flowing tap water, and a stir bar A 200 mL three-necked flask was charged with 100.0 g (0.47 mol) of 1,1,1,3,3-pentachloropropane (240fa) with a purity of 98.6FID% and 0.1 g (0.6 mmol) of AIBN. Agitation was started. The top of the Dimroth was connected to a 500 mL-PFA container containing a 1 LPFA water trap and then 250 g of 25 wt% potassium hydroxide aqueous solution using a PFA tube. The flask was heated to 60 ° C. in an oil bath, and 34 g (0.48 mol) of chlorine was introduced from the ball filter over 200 minutes. After introducing chlorine, the reactor was cooled to complete the reaction. The kettle residue in the flask was washed with water and a weak alkaline aqueous solution to recover 114 g of organic matter.
The results of analyzing the collected organic matter by gas chromatography are shown below:
1,1,1,3,3,3-hexachloropropane (230fa): 51.3FID%;
1,1,1,2,3,3-hexachloropropane (230 da): 10.8 FID%;
1,1,1,3,3-pentachloropropane (240fa): 29.2FID%;
Two heptachloropropane isomers (220 isomers): 7.1 FID%;
Other compounds: 1.6 FID%.

As shown in Examples 5-1 to 5-3, 1,1,1,3,3,3-hexa obtained by chlorination of 1,1,1,3,3-pentachloropropane (240fa) The 1,1,3,3,3-pentachloropropene (1220za) can also be obtained by subjecting the reaction product containing chloropropane (230fa) to the dehydrochlorination of 230fa without purification.

(A-2) Gas phase fluorination of 1220za [Example 7-1]
A 1 inch, 40 cm long cylindrical stainless steel (SUS316) reaction tube equipped with an electric furnace is filled with 50 mL of Raschig ring (SUS316L, 5Φ × 5 mm), and nitrogen gas is allowed to flow at a flow rate of about 30 cc / min. The temperature was raised to 240 ° C. Nitrogen feed was stopped and vaporized 1,1,3,3,3-pentachloropropene (1220za) raw material was introduced at a flow rate of 0.110 g / min and hydrogen fluoride at a flow rate of 0.120 g / min (contact with packing) Time: 20 seconds). When the flow rate was stabilized, a 500 mL water trap cooled with ice water was installed at the outlet of the reaction tube to collect organic matter and absorb by-product acid content for about 100 minutes. The slipped gas component was collected with a dry ice strap, and the weight recovery rate was calculated together with the ice water trap. The organic component from which the acid was removed was analyzed by gas chromatography.

[Example 7-2]
The same operation as in Example 7-1 was performed except that the temperature in the reaction tube was raised to 270 ° C.

[Example 7-3]
The same operation as in Example 7-1 was performed except that the temperature in the reaction tube was raised to 300 ° C.

Table 5 shows the results of Examples 7-1 to 7-3. In Table 5, “-” indicates that no detection was made.

[Example 8-1]
The same operation as in Example 7-1 was performed except that activated carbon was filled instead of the Raschig ring.

[Example 8-2]
The same operation as in Example 7-1 was performed, except that a fluorinated alumina catalyst (hereinafter also referred to as catalyst 1) was filled instead of Raschig ring. In addition, the catalyst 1 used what was prepared according to the following catalyst preparation examples 1.

[Example 8-3]
Except for filling fluorinated chromium-supported activated carbon (hereinafter also referred to as catalyst 2) instead of Raschig ring, and introducing chlorine together with the raw material and hydrogen fluoride at a flow rate of 0.005 g / min. The same operation as in 7-1 was performed. Catalyst 2 was prepared according to Catalyst Preparation Example 2 below.

Table 6 shows the results of Examples 8-1 to 8-3. In Table 6, “-” indicates that no detection was made.

[Example 9-1]
Except for introducing 1,1,3,3,3-pentachloropropene (1220za) raw material at a flow rate of 0.200 g / min and hydrogen fluoride at a flow rate of 0.125 g / min (contact time with packing: 20 seconds) The same operation as in Example 1-1 was performed.

[Example 9-2]
The same operation as in Example 9-1 was performed except that activated carbon was filled instead of the Raschig ring.

[Example 9-3]
The same operation as in Example 7-1 was performed except that catalyst 2 was filled instead of Raschig ring and chlorine was introduced at a flow rate of 0.005 g / min together with the raw material and hydrogen fluoride.

Table 7 shows the results of Examples 9-1 to 9-3. In Table 7, “-” indicates that no detection was made.

[Catalyst Preparation Example 1]
300 g of activated alumina (KHS-46 manufactured by Sumitomo Chemical Co., Ltd .: particle size 4 to 6 mm, specific surface area 155 m ² / g) was weighed, and the powder adhering to the surface was washed with water. To the washed alumina, 1150 g of a 10 wt% hydrogen fluoride aqueous solution was slowly added, and the mixture was stirred and then allowed to stand for about 4 hours. After washing with water, it was filtered, dried at room temperature overnight, and then dried at 200 ° C. for 2 hours in an electric furnace. 150 mL of this dried activated alumina was put into a stainless steel (SUS316) reaction tube having an inner diameter of 1 inch and a length of 40 cm, and heated to 200 ° C. in an electric furnace while flowing nitrogen at 150 cc / sec. .1 g / min. Although the temperature rises as the hydrogen fluoride treatment is performed, the flow rates of nitrogen and hydrogen fluoride are adjusted so that the internal temperature does not exceed 400 ° C. When the exotherm subsided, the flow rate of nitrogen was reduced to 30 cc / sec, the electric furnace set temperature was raised by 50 ° C. every 30 minutes, finally raised to 400 ° C., and this state was maintained for 2 hours. Thus, a fluorinated alumina catalyst (catalyst 1) was prepared.

[Catalyst Preparation Example 2]
A 20% by mass chromium chloride aqueous solution was prepared in an Erlenmeyer flask, and 100 mL of activated carbon (Shirakaba G2X) was immersed therein and held for 3 hours. The residue obtained by filtering this was dried at 70 ° C. under reduced pressure using a rotary evaporator. 100 mL of the chromium-supported activated carbon thus obtained was charged into a 1-inch-long cylindrical stainless steel (SUS316) reaction tube equipped with an electric furnace, heated to 200 ° C. while flowing nitrogen gas, The flow rate of nitrogen and hydrogen fluoride is adjusted so that the internal temperature does not exceed 400 ° C by entraining 0.1 g / sec of hydrogen fluoride (HF) with 150 cc / sec of nitrogen gas. did. When the hot spot due to the fluorination of the loaded chromium-supported activated carbon reaches the outlet end of the reaction tube, the flow rate of nitrogen is reduced to 30 cc / second, and the set temperature of the electric furnace is increased by 50 ° C. every 30 minutes. The temperature was raised to 400 ° C. and the state was maintained for 2 hours. Thus, fluorinated chromium-supported activated carbon (catalyst 2) was prepared.

Claims (17)

1. And fluorinating 1,1,3,3,3-pentachloropropene with hydrogen fluoride to produce 1,1-dichloro-3,3,3-trifluoropropene. , 1-Dichloro-3,3,3-trifluoropropene production method.
2. The method according to claim 1, wherein the amount of the hydrogen fluoride used is 3 to 40 mol per 1 mol of 1,1,3,3,3-pentachloropropene.
3. The method according to claim 1 or 2, wherein the fluorination is performed in a liquid phase.
4. The method according to claim 3, wherein the fluorination is performed at 0 to 200 ° C.
5. By the fluorination, 1,1-dichloro-3,3,3-trifluoropropene and 1,1,3-trichloro-3,3-difluoropropene or 1,1-dichloro-1,3,3,3 -Process according to claim 3 or 4, characterized in that tetrafluoropropane is produced.
6. The method according to claim 1 or 2, wherein the fluorination is performed in a gas phase.
7. The method according to claim 6, wherein the fluorination is performed at 100 to 500 ° C.
8. The method according to any one of claims 1 to 7, wherein the fluorination is performed at 0 to 10 MPaG.
9. The method according to any one of claims 1 to 8, wherein the fluorination is carried out in the presence or absence of a catalyst.
10. The method according to any one of claims 1 to 9, comprising a step of purifying 1,1-dichloro-3,3,3-trifluoropropene.
11. 1,1,3,3,3-pentachloropropene and 1,1,3,3-tetrachloro-3-fluoropropene or 1,1,3-trichloro-3,3-difluoropropene are subjected to the fluorination The method according to any one of claims 1 to 10, characterized in that:
12. Fluorinating 1,1,3,3,3-pentachloropropene with hydrogen fluoride to produce 1,1,3-trichloro-3,3-difluoropropene, A method for producing 1,3-trichloro-3,3-difluoropropene.
13. The method according to claim 12, wherein the fluorination is performed in a liquid phase.
14. The method according to claim 12 or 13, characterized in that the fluorination is carried out in the presence or absence of a catalyst.
15. The fluorination produces 1,1-dichloro-3,3,3-trifluoropropene together with 1,1,3-trichloro-3,3-difluoropropene. 14. The method according to any one of 14.
16. Dehydrochlorination of 1,1,1,3,3,3-hexachloropropane in the liquid phase to obtain 1,1,3,3,3-pentachloropropene in the presence of a Lewis acid catalyst The method according to any one of claims 1 to 15, further comprising a crystallization step.
17. Chlorination of 1,1,1,3,3-pentachloropropane in the liquid phase to give 1,1,1,3,3,3-hexachloropropane under UV irradiation or in the presence of a radical initiator The method according to claim 16, further comprising a crystallization step.