CN115996902A - Process for producing hydrochlorofluorocarbon - Google Patents

Process for producing hydrochlorofluorocarbon Download PDF

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CN115996902A
CN115996902A CN202180053719.XA CN202180053719A CN115996902A CN 115996902 A CN115996902 A CN 115996902A CN 202180053719 A CN202180053719 A CN 202180053719A CN 115996902 A CN115996902 A CN 115996902A
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fluorine
reaction
containing alcohol
chlorinating agent
production process
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岩濑卓也
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AGC Inc
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Asahi Glass Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine

Abstract

The present invention provides a method for producing a hydrochlorofluorocarbon with a high yield and high purity, with a small amount of by-products. The method is a method for producing a hydrochlorofluorocarbon wherein a fluorine-containing alcohol is reacted with a chlorinating agent in the presence of a catalyst, and the hydroxyl group of the fluorine-containing alcohol is replaced with a chlorine atom, wherein the catalyst is phosphine oxide, and at least one chlorinating agent selected from thionyl chloride, oxalyl chloride and phosgene is used as the chlorinating agent.

Description

Process for producing hydrochlorofluorocarbon
Technical Field
The present invention relates to a process for producing a hydrochlorofluorocarbon.
Background
Hydrochlorofluorocarbons (hereinafter also referred to as HCFCs) are used as new cleaning agents, refrigerants, blowing agents and aerosols, or synthetic raw materials thereof. For example, HCFCs are sometimes used as a raw material for synthesizing hydrochlorofluoroolefins (hereinafter also referred to as HCFCs). Specifically, for example, patent document 1 describes that 3-chloro-1, 2-tetrafluoropropane (HCFC-244 ca, hereinafter also referred to as 244 ca) is used as a synthetic raw material for producing 1-chloro-2, 3-trifluoropropene (HCFO-1233 yd, hereinafter also referred to as 1233 yd). Patent document 2 describes 5-chloro-1, 2,3, 4-octafluoropentane (HCFC-448 occc, hereinafter also referred to as 448 occc) is used as a synthetic raw material for producing 1-chloro-2, 3,4, 5-heptafluoropentene (HCFO-1437 dycc, hereinafter also referred to as 1437 dycc).
Prior art literature
Patent literature
Patent document 1: international publication No. 2018/131394
Patent document 2: international publication No. 2019/124220
Disclosure of Invention
Technical problem to be solved by the invention
HCFCs can be obtained by reacting a fluorine-containing alcohol with a chlorinating agent. However, in the method for producing HCFCs described in the prior art, a compound obtained by adding two molecules of a fluorinated alcohol to a chlorinating agent (hereinafter also referred to as a fluorinated alcohol adduct) and the like are produced together with the target HCFCs as by-products. Thus, it is desirable to convert such by-products to HCFCs after chlorination.
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing HCFC with a low yield and high purity, with a small amount of byproducts.
Technical proposal adopted for solving the technical problems
In order to solve the above technical problems, the present inventors have conducted intensive studies and have found that the above technical problems can be solved by the following technical means.
(1) A process for producing a hydrochlorofluorocarbon, which comprises reacting a fluorine-containing alcohol with a chlorinating agent in the presence of a catalyst, wherein the catalyst is phosphine oxide, and at least one chlorinating agent selected from thionyl chloride, oxalyl chloride and phosgene is used as the chlorinating agent.
(2) The process according to (1), wherein the fluorine-containing alcohol is a compound represented by the following formula (1), X-R f -CH 2 OH(1)
Wherein X represents a hydrogen atom or a fluorine atom, R f Represents a fluoroalkylene having 1 or more carbon atomsA base.
(3) The production method according to (1) or (2), wherein the fluorine-containing alcohol is 2,3, tetrafluoropropanol or 2,3,4, 5-octafluoropentanol.
(4) The process according to any one of (1) to (3), wherein the phosphine oxide is a compound represented by the following formula (2),
[ chemical 1]
Figure BDA0004101433060000021
Wherein R is 1 、R 2 、R 3 Each independently represents a monovalent hydrocarbon group which may have a substituent or a monovalent nitrogen-containing heterocyclic group which may have a substituent, wherein a carbon atom forming a ring is bonded to a phosphorus atom.
(5) The method according to (4), wherein R 1 ～R 3 Are all phenyl groups, or R 1 And R is 2 Is phenyl, R 3 Is pyridyl, or R 1 ～R 3 Are each 4-fluorophenyl, or R 1 ～R 3 All are 2-tolyl groups.
(6) The production method according to any one of (1) to (5), wherein the chlorinating agent is thionyl chloride or oxalyl chloride.
(7) The production method according to any one of (1) to (6), wherein the reaction does not contain an alcohol other than the fluorine-containing alcohol.
(8) The production method according to any one of (1) to (7), wherein the content of the fluorine-containing alcohol adduct contained in the reaction solution obtained by the reaction is 10% by mass or less relative to the total amount of the reaction solution.
(9) The production method according to any one of (1) to (8), wherein the reaction temperature in the reaction is 0 to 150 ℃.
(10) The production method according to any one of (1) to (9), wherein the reaction time of the reaction is 2 to 8 hours.
(11) The production process according to any one of (1) to (10), wherein the reaction is carried out in a molar ratio of the chlorinating agent to the fluorine-containing alcohol (chlorinating agent/fluorine-containing alcohol) of 0.01 to 100.
(12) The production process according to any one of (1) to (11), wherein the reaction is carried out in a molar ratio of the phosphine oxide to the fluorine-containing alcohol (phosphine oxide/fluorine-containing alcohol) of 0.0001 to 10.
(13) A process for producing a hydrochlorofluoroolefin, which comprises subjecting a hydrochlorofluorocarbon produced by the production process according to any one of (1) to (12) to a dehydrofluorination reaction in the presence of a base and/or a catalyst.
(14) The method according to (13), wherein, the hydrochlorofluorocarbon is 3-chloro-1, 2-tetrafluoro propane or 5-chloro-1, 2,3, 4-octafluoropentane.
(15) The production process according to (13) or (14), wherein the hydrochlorofluoroolefin is 1-chloro-2, 3-trifluoropropene or 1-chloro-2, 3,4, 5-heptafluoropentene.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a process is provided which can produce HCFCs in high yield and high purity with a small amount of by-products.
Detailed Description
The process for producing HCFC of the present invention (hereinafter also referred to simply as "the process of the present invention") is characterized by reacting a fluorine-containing alcohol with a specific chlorinating agent in the presence of phosphine oxide as a catalyst. The hydroxyl group of the fluorine-containing alcohol is replaced by a chlorine atom by the reaction of the fluorine-containing alcohol and a specific chlorinating agent to produce HCFC.
The production method of the present invention can produce HCFC with a high yield and high purity with a small amount of by-products.
The components used in the production method of the present invention will be described in detail first, and the steps of the production method will be described in detail.
(fluorine-containing alcohol)
In the production method of the present invention, a fluorine-containing alcohol is used as a raw material. The fluorine-containing alcohol as the raw material may be a mixture of 2 or more fluorine-containing alcohols. That is, the production method of the present invention is industrially advantageous because it can produce 2 or more types of HCFCs simultaneously.
The fluorine-containing alcohol used in the production method of the present invention is not particularly limited, and from the viewpoint of reactivity, a primary alcohol, that is, a compound represented by the following formula (1), is preferable.
X-R f -CH 2 OH(1)
Wherein X represents a hydrogen atom or a fluorine atom, R f Represents a fluorinated alkylene group having 1 or more carbon atoms.
R f The carbon number of (2) is preferably 1 to 7, more preferably 1 to 5, still more preferably 1 to 4, particularly preferably 2 to 4.R is R f The hydrogen atom may be contained, and is preferably a perfluoroalkylene group, and particularly preferably a linear perfluoroalkylene group.
As the fluorine-containing alcohol, there is used, examples thereof include 2, 2-trifluoroethanol, 2, 3-tetrafluoropropanol (hereinafter also abbreviated as TFPO) 2, 3-pentafluoropropanol, 2,3, 4-heptafluorobutanol 2, 3-pentafluoropropanol 2,3, 4-heptafluorobutanol.
As the fluorine-containing alcohol, there is used, preferably 2, 2-trifluoroethanol, TFPO, 2, 3-pentafluoropropanol, 2,3, 4-heptafluorobutanol 2,3, 4-hexafluorobutanol, OFPO or 3,4, 5, 6-nonafluorohexanol, more preferably TFPO, 2, 3-pentafluoropropanol 2,3, 4-heptafluorobutanol, 2,3, 4-hexafluorobutanol or OFPO, TFPO or OFPO is particularly preferred.
When a fluoroalcohol is used, it may also be a mixture with other compounds. That is, the raw material of the production method of the present invention may contain a fluorine-containing alcohol, and for example, a mixture of a fluorine-containing alcohol and other compounds may be used as the raw material.
Examples of the other compounds contained in the raw materials used in the production method of the present invention include impurities such as raw materials for producing a fluorine-containing alcohol and by-products other than the fluorine-containing alcohol produced in the production of the fluorine-containing alcohol. When the raw material contains the above-mentioned impurities, by-products produced from the impurities can be removed by a known method such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-layer separation, adsorption, etc. As the impurities, compounds inert in the production method of the present invention are preferable.
The raw material preferably contains a fluorine-containing alcohol as a main component. The content of the fluorine-containing alcohol is preferably 50 mass% or more, more preferably 75 mass% or more, further preferably 80 mass% or more, and particularly preferably 90 mass% or more, relative to the total mass of the raw materials. The upper limit is 100 mass%.
In the reaction of the fluorine-containing alcohol with the specific chlorinating agent, it is preferable that alcohols other than the fluorine-containing alcohol are not contained in view of improving the selectivity of HCFC. The amount of the alcohol other than the fluorine-containing alcohol is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and still more preferably 100 mass ppm or less, relative to the total amount of the fluorine-containing alcohol.
(chlorinating agent)
The chlorinating agent used in the production method of the present invention is at least one chlorinating agent selected from thionyl chloride, oxalyl chloride and phosgene from the viewpoint of reactivity with a catalyst described later.
As the chlorinating agent, a mixture of 2 or more kinds may be used.
As the chlorinating agent, thionyl chloride and oxalyl chloride are preferable from the viewpoint of more efficient production of HCFCs.
In the production method of the present invention, the molar ratio of the chlorinating agent to the fluorine-containing alcohol used (the molar amount of the chlorinating agent/the molar amount of the fluorine-containing alcohol) is preferably 0.01 to 100, more preferably 0.05 to 50, still more preferably 0.1 to 10, particularly preferably 0.5 to 5, from the viewpoint of more efficient production of HCFCs. If it is within the above range, the production of by-products is suppressed and the volumetric efficiency of the reactor is improved.
(catalyst)
The phosphine oxide of the catalyst in the production method of the present invention is preferably phosphine oxide of the compound represented by the following formula (2).
[ chemical 2]
Figure BDA0004101433060000051
In the formula (2), R 1 、R 2 、R 3 Each independently represents a monovalent hydrocarbon group which may have a substituent or a monovalent nitrogen-containing heterocyclic group which may have a substituent, whereinThe carbon atoms of the ring are bonded to phosphorus atoms.
Examples of the monovalent hydrocarbon group include monovalent aliphatic hydrocarbon groups such as alkyl, alkenyl and alkynyl groups, monovalent alicyclic hydrocarbon groups such as cycloalkyl and cycloalkenyl groups, and aryl groups such as phenyl groups. The carbon number-removed substituent of the monovalent hydrocarbon group is preferably 8 or less, more preferably 6 or less.
Examples of the substituent that the monovalent aliphatic hydrocarbon group may have include a monovalent alicyclic hydrocarbon group, an aryl group, a monovalent heterocyclic group, a halogen atom such as a fluorine atom, and an alkoxy group. Examples of the substituent that the monovalent alicyclic hydrocarbon group may have include a monovalent alicyclic hydrocarbon group, an aryl group, a monovalent heterocyclic group, a halogen atom such as a fluorine atom, and an alkoxy group. Examples of the substituent that the aryl group may have include a monovalent alicyclic hydrocarbon group, a monovalent heterocyclic group, a halogen atom such as a fluorine atom, and an alkoxy group.
Examples of the monovalent nitrogen-containing heterocyclic group include heterocyclic groups having 1 or 2 nitrogen atoms such as pyridyl and imidazolyl. Examples of the substituent that the monovalent nitrogen-containing heterocyclic group may have include a monovalent alicyclic hydrocarbon group, an aryl group, and a halogen atom such as a fluorine atom.
In the production method of the present invention, R is a group for producing HCFC more efficiently 1 、R 2 、R 3 Each independently is preferably phenyl, pyridyl, 4-fluorophenyl, 2-tolyl, methyl, butyl or 3-methylcyclopentenyl, more preferably phenyl, pyridyl, 4-fluorophenyl or 2-tolyl, further preferably phenyl, pyridyl or 4-fluorophenyl, particularly preferably phenyl.
Specifically, R is preferably 1 ～R 3 Are all phenyl groups, or R 1 And R is 2 Is phenyl, R 3 Is pyridyl, or R 1 ～R 3 Are each 4-fluorophenyl, or R 1 ～R 3 All are 2-tolyl groups. More preferably R 1 ～R 3 Are all phenyl groups, or R 1 And R is 2 Is phenyl, R 3 Is pyridyl, or R 1 ～R 3 Are all 4-fluorophenyl groups, R being particularly preferred 1 ～R 3 All are phenyl groups.
In the production method of the present invention, the molar ratio of the phosphine oxide to the fluorine-containing alcohol used (molar amount of phosphine oxide/molar amount of fluorine-containing alcohol) is preferably 0.0001 to 10, more preferably 0.001 to 5, still more preferably 0.01 to 1, particularly preferably 0.1 to 0.5, from the viewpoint of obtaining a sufficient reaction rate.
In the production method of the present invention, phosphine oxide is preferably used by dissolving in a reaction component or an inert solvent. From the viewpoint of reducing the waste liquid, it is preferably used by dissolving it in a fluorine-containing alcohol or a chlorinating agent.
(manufacturing method)
In the production method of the present invention, a fluorine-containing alcohol is brought into contact with a chlorinating agent in the presence of phosphine oxide using a reactor.
The shape and structure of the reactor are not particularly limited as long as the reactor can be charged with a fluorine-containing alcohol and a chlorinating agent to react. Examples of such a reactor include a glass reactor, a SUS reactor, a glass-lined reactor, and a resin-lined reactor. The temperature adjusting unit may be any means capable of adjusting the reaction temperature of the fluorine-containing alcohol and the chlorinating agent. Such means may be an oil bath. Further, the temperature adjusting portion may be provided integrally with the reactor.
The production method of the present invention can be carried out either in a gas phase reaction or a liquid phase reaction, and is preferably carried out in a liquid phase reaction, because it is more advantageous to the industrial implementation. The liquid phase reaction is carried out by bringing each of the fluorine-containing alcohol and the chlorinating agent into a liquid state in the presence of phosphine oxide.
As a specific step of the gas phase reaction, there is a step of supplying a raw material fluorine-containing alcohol heated to a gaseous state and a chlorinating agent to a reactor, and bringing phosphine oxide and a gaseous fluorine-containing alcohol filled in the reactor into contact with the chlorinating agent to obtain HCFC.
From the viewpoint of being effective in adjusting the flow rate, suppressing by-products, suppressing catalyst deactivation, and the like, a gas (diluent gas) inert to the above reaction may be supplied to the reactor. Specific examples of the diluent gas include nitrogen, carbon dioxide, helium and argon.
Specific examples of the liquid phase reaction include a step of dissolving phosphine oxide in a fluorine-containing alcohol or a chlorinating agent in advance, and a step of bringing a liquid fluorine-containing alcohol into contact with a liquid chlorinating agent by stirring or the like to obtain HCFC. Preferably, the phosphine oxide is dissolved in the chlorinating agent, and the liquid fluorine-containing alcohol is brought into contact with the liquid chlorinating agent by stirring or the like.
The liquid fluorine-containing alcohol, the catalyst and the chlorinating agent may be added to the reactor at the same time and the reactor may be heated after the addition, or the fluorine-containing alcohol may be added after the reactor to which the catalyst and the chlorinating agent are added is heated. In order to control the sulfur dioxide gas and the hydrogen chloride gas generated at the start of the reaction, it is preferable to control the addition rate.
Among them, the latter liquid phase reaction is preferred from the viewpoints of reaction temperature, reaction time, reaction yield and HCFC selectivity. In addition, in the case of carrying out the production method of the present invention in a liquid phase reaction, a smaller-sized reactor can be used as compared with a gas phase reaction, which is preferable from the viewpoint.
The reaction temperature (temperature in the reactor) in the production process of the present invention is preferably 0 to 150 ℃, more preferably 10 to 125 ℃, and even more preferably 20 to 100 ℃, from the viewpoint of more efficient production of HCFCs. If the reaction temperature does not reach the above range, the reaction rate and reaction yield may be lowered, and the conversion of the fluorine-containing alcohol tends to be lowered with the excessive amount of unreacted fluorine-containing alcohol remaining. On the other hand, when the reaction temperature exceeds the above range, the fluorine-containing alcohol adduct is excessively produced, and the selectivity of HCFC tends to be low.
The temperature within the reactor may be controlled by adjusting the temperature and pressure of the feed to the reactor. The inside of the reactor may be heated with assistance of an electric heater, a microwave generator, or the like, as needed.
The production process of the present invention may be carried out in a batch manner or a continuous manner. In the case of the batch system, one of the predetermined amounts of the fluorine-containing alcohol and the chlorinating agent is placed in the reactor as a material to be supplied, and the other is gradually added to the material to be supplied in the reactor, whereby the production is performed. For example, the method can be carried out by placing a predetermined amount of a chlorinating agent as a material to be supplied into a reactor and then gradually adding a fluorine-containing alcohol to the chlorinating agent, or by placing a predetermined amount of a fluorine-containing alcohol as a material to be supplied into a reactor and then gradually adding a chlorinating agent to the fluorine-containing alcohol. In this case, the phosphine oxide is preferably premixed with the fluorine-containing alcohol or the chlorinating agent. All of the prescribed amount of phosphine oxide may be mixed into either of the fluorine-containing alcohol and the chlorinating agent. The phosphine oxide may be separately mixed into the fluorine-containing alcohol and the chlorinating agent in a predetermined amount.
In the case of the continuous method, the fluorine-containing alcohol, the chlorinating agent and the phosphine oxide are continuously fed into the reactor at a predetermined feeding rate in a predetermined molar ratio, and are brought into contact with each other in the reactor for a predetermined time, whereby the catalyst is produced. In this case, from the viewpoint of operation efficiency, the phosphine oxide is preferably premixed with the fluorine-containing alcohol or the chlorinating agent and then fed into the reactor. When the production method of the present invention is carried out in a continuous manner, the feed rates of the fluorine-containing alcohol, the chlorinating agent and the phosphine oxide to the reactor can be adjusted according to the feed flow rate of each compound or the sulfur dioxide gas or the hydrogen chloride gas generated during the reaction.
The reaction time in the production method of the present invention is, for example, 2 to 8 hours, depending on the amounts of phosphine oxide, fluorine-containing alcohol and chlorinating agent. The reaction time in the production method of the present invention is expressed as the contact time between the fluorine-containing alcohol and the chlorinating agent. For example, in the case of manufacturing the hydrogen chloride gas by intermittently feeding one of the predetermined amounts of the fluorine-containing alcohol and the chlorinating agent as the material to be fed into the reactor and gradually adding the other to the material to be fed into the reactor as described above, the reaction time is a time from when the supply of the one of the fluorine-containing alcohol and the chlorinating agent as the material to be fed is started to the other until the hydrogen chloride gas stops being produced and the reaction is completed. In the case where the production process of the present invention is carried out in a continuous manner, the reaction time is the residence time of the fluorine-containing alcohol and the chlorinating agent in the reactor.
In the case where the production process of the present invention is carried out as a liquid phase reaction, it is preferable to contact the HCFC-containing reaction product mixture with an aqueous alkali solution to neutralize hydrogen chloride and sulfur dioxide in the HCFC-containing reaction product mixture. The alkaline aqueous solution used in this case may be, for example, an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. After contact with the aqueous alkaline solution, the HCFC-containing reaction product mixture is allowed to stand to separate the organic and aqueous phases. Since HCFCs are contained in the organic phase, HCFCs can be obtained by separating and recovering the organic phase.
The organic layer liquid obtained may contain, for example, phosphine oxide, unreacted raw materials such as a fluorine-containing alcohol and a chlorinating agent, a fluorine-containing alcohol adduct as a by-product, a by-product derived from a fluorine-containing alcohol other than the fluorine-containing alcohol adduct, and the like in addition to HCFC. However, when the production method of the present invention is employed, the fluorine-containing alcohol adduct is usually not contained.
The organic layer solution containing the unreacted raw materials and by-products is preferably separated and purified by conventional distillation or the like as needed to obtain HCFC having less unreacted raw materials and by-products.
The reaction liquid obtained by purification as needed preferably contains HCFC as a main component. The HCFC content is preferably 80 mass% or more, more preferably 90 mass% or more, and even more preferably 95 mass% or more, based on the total mass of the reaction solution. The upper limit is, for example, 100 mass%.
The HCFC obtained by the production method of the present invention can be produced by dehydrofluorination reaction. Specifically, HCFCs obtained by the production method of the present invention are subjected to dehydrofluorination in the presence of a base and/or a catalyst to produce HCFCs.
When the raw material for producing HCFO contains a fluorine-containing alcohol adduct, the fluorine-containing alcohol adduct is decomposed into fluorine-containing alcohol in the reactor and reacts with HCFO as a product, and the selectivity of HCFO may be lowered.
The content of the fluorine-containing alcohol adduct contained in the HCFC-containing reaction solution obtained by the reaction of the fluorine-containing alcohol and the chlorinating agent is preferably 10 mass% or less, more preferably 5 mass% or less, and particularly preferably 1 mass% or less, relative to the total amount of the HCFC-containing reaction solution. Most preferably, the fluorine-containing alcohol adduct is absent. The production method of the present invention is preferably used for the production of HCFO because the production of byproducts can be suppressed.
In the present specification, without particular distinction, a compound name or a compound abbreviation means at least one selected from the group consisting of Z isomers and E isomers, more specifically, Z isomers or E isomers or a mixture of Z isomers and E isomers in any ratio. When (E) or (Z) is added after the compound name or compound abbreviation, the (E) isomer or (Z) isomer of the corresponding compound is represented, respectively. For example, 1233yd (Z) represents Z isomer, and 1233yd (E) represents E isomer.
In the production method of the present invention, 244ca was obtained when the fluorine-containing alcohol was TFPO.
The reaction solution contained 244ca as a main component. The components other than 244ca can be removed to a desired extent by a known method such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-layer separation, adsorption, and the like.
The 244ca obtained may be subjected to dehydrofluorination reaction to produce 1233yd.
As a step of dehydrofluorination, a known method such as International publication No. 2016/136744 can be exemplified.
The dehydrofluorination reaction of 244ca may be either a liquid-phase reaction or a gas-phase reaction. The liquid phase reaction refers to dehydrofluorination reaction of 244ca in a liquid or dissolved in a liquid. And the gas phase reaction refers to dehydrofluorination reaction by which the gaseous 244ca is allowed to proceed.
In the production method of the present invention, 448occc was obtained when the fluorine-containing alcohol was OFPO.
The reaction solution contained 448occc as a main component. Components other than 448occc can be removed to a desired extent by a known method such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-layer separation, or adsorption.
The resulting 448occc may be subjected to dehydrofluorination reaction to produce 1437dycc. Particularly preferably 1437dycc (Z).
As a step of dehydrofluorination reaction, zhurnal Organicheskoi Khimii,
(Russia), 1988, vol.24, no.8, pp.1626-1633, etc.
The dehydrofluorination reaction of 448occc may be either a liquid phase reaction or a gas phase reaction. The liquid phase reaction refers to dehydrofluorination reaction by 448occ in liquid or dissolved in liquid. And the gas phase reaction refers to dehydrofluorination reaction by bringing gaseous 448occc.
Examples
The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Examples 1 to 3, 6, 8 and 9 are examples of the present invention, and examples 4,5 and 7 are comparative examples.
Example 1
A four-necked flask (reactor) equipped with a stirrer and a glass distillation column (measurement of number of plates: 5) packed with Raschig rings and a Dimu Luo Lengning reactor was immersed in an oil bath as a reaction apparatus. To which triphenylphosphine oxide (in the above formula (2), R 1 ～R 3 Are all phenyl) (hereinafter also referred to as Ph 3 PO) (5.27 g), thionyl chloride (49.5 g), TFPO (50.0 g), and the temperature of the oil bath was adjusted to 80 ℃. The TFPO was converted to 244ca and distilled to obtain a distillate containing 244ca. The ratio of reflux time/distillation time (sec/sec) was set to 10/1 by a reflux timer.
Then, the distillate was brought into contact with a 10 mass% aqueous potassium hydroxide solution to neutralize sulfur dioxide gas and the like in the distillate, and an organic phase portion was recovered from the neutralized distillate to analyze the composition thereof. Analysis was performed using Gas Chromatography (GC). The column was used with DB-1301 (length 60 m. Times. Inner diameter 250. Mu.m. Times. Thickness 1. Mu.m, manufactured by Agilent technologies Co., ltd. (Agilent Technologies)).
In addition, by 1 H-NMR 19 C-NMR (JNM-EC P400, manufactured by Japanese electronics Co., ltd.) analyzed the reaction solution remaining in the reactor. The results are shown in Table 1.
Example 2
A four-necked flask (reactor) equipped with a stirrer and a glass distillation column (measurement of number of plates: 5) packed with Raschig rings and a Dimu Luo Lengning reactor was immersed in an oil bath as a reaction apparatus. The reaction was carried out in the same manner as in example 1 except that OFPO was used as a raw material instead of TFPO, and the results are shown in table 1.
Example 3
A four-necked flask (reactor) equipped with a stirrer and a glass distillation column (measurement of number of plates: 5) packed with Raschig rings and a Dimu Luo Lengning reactor was immersed in an oil bath as a reaction apparatus. The reaction was carried out in the same manner as in example 1 except that oxalyl chloride was used as a chlorinating agent instead of thionyl chloride, and the results are shown in Table 1.
Example 4
(step 1)
A four-necked flask (reactor) equipped with a stirrer and a glass distillation column (measurement of number of plates: 5) packed with Raschig rings and a Dimu Luo Lengning reactor was immersed in an oil bath as a reaction apparatus. Then, after thionyl chloride was charged into the four-necked flask, a mixed solution of TFPO and N, N-dimethylformamide (hereinafter also referred to as DMF) was added dropwise to the four-necked flask. The temperature of the oil bath and the dropping speed of the mixed solution were adjusted so that the reaction temperature (liquid phase temperature in the four-necked flask) at the time of dropping the mixed solution was 0 ℃. After the addition of the mixture was completed, stirring was continued until the hydrogen chloride gas was stopped, and a reaction product mixture containing 2, 3-tetrafluoropropane sulfonyl chloride was recovered.
(step 2)
In the same reaction apparatus as in step 1, 40g of DMF was charged into a four-necked flask, and then the four-necked flask was heated to 120℃while cooling the Dim Luo Lengning apparatus to-20 ℃. The reaction product mixture containing 2, 3-tetrafluoropropane sulfonyl chloride obtained in step 1 was fed at a rate of 75g/hr using a liquid feed pump, and then the reactor (four-necked flask) was cooled to room temperature to complete the reaction. Thereby, 2, 3-tetrafluoropropane sulfonyl chloride was thermally decomposed while being distilled to obtain a distillate containing 244ca. The ratio of reflux time/distillation time (sec/sec) was set to 5/1 by a reflux timer.
Then, the sulfur dioxide gas remaining in the distillate was neutralized with a 20 mass% aqueous potassium hydroxide solution. A part of the organic phase was recovered from the neutralized distillate and analyzed for its composition. The results are shown in Table 1.
Example 5
(step 1)
A four-necked flask (reactor) equipped with a stirrer and a glass distillation column (measurement of number of plates: 5) packed with Raschig rings and a Dimu Luo Lengning reactor was immersed in an oil bath as a reaction apparatus. Then, after thionyl chloride was charged into the four-necked flask, the mixed solution of OFPO and DMF was dropped into the four-necked flask. The temperature of the oil bath and the dropping speed of the mixed solution were adjusted so that the reaction temperature (liquid phase temperature in the four-necked flask) at the time of dropping the mixed solution was 50 ℃. After the addition of the mixed solution was completed, stirring was continued until the hydrogen chloride gas was stopped, and a reaction product mixture containing 2,3,4, 5-octafluoropentanesulfonyl chloride was recovered.
(step 2)
In the same reaction apparatus as in step 1, 40g of DMF was charged into a four-necked flask, and then the four-necked flask was heated to 130℃while cooling the Dim Luo Lengning apparatus to-20 ℃. The reaction product mixture containing 2,3,4, 5-octafluoropentanesulfonyl chloride obtained in step 1 was fed at a rate of 75g/hr using a liquid feed pump, and the reactor (four-necked flask) was cooled to room temperature to complete the reaction. Thereby, 2,3,4, 5-octafluoropentanesulfonyl chloride was thermally decomposed while being distilled to obtain a distillate containing 448occc. The ratio of reflux time/distillation time (sec/sec) was set to 5/1 by a reflux timer.
Then, the sulfur dioxide gas remaining in the distillate was neutralized with a 20 mass% aqueous potassium hydroxide solution. A part of the organic phase was recovered from the neutralized distillate and analyzed for its composition. The results are shown in Table 1.
The conversion in tables 1 and 2 represents the ratio (%) of the molar amount consumed in the reaction to the amount of feed (molar amount), and the selectivity represents the ratio of the molar amount consumed to the molar amount of raw material consumed for the formation of each compound. The chlorinating agent amount (mol/mol) represents the molar ratio of chlorinating agent to fluorine-containing alcohol. The amount of catalyst (mol/mol) represents the molar ratio of catalyst to fluorine-containing alcohol.
TABLE 1
Example 1 Example 2 Example 3 Example 4 Example 5
Fluorine-containing alcohol TFPO OFPO TFPO TFPO OFPO
Chlorinating agent SOCl 2 SOCl 2 (ClCO) 2 SOCl 2 SOCl 2
Chlorinating dose (mol/mol) 1.1 1.1 1.1 1.1 1.1
Catalyst Ph 3 PO Ph 3 PO Ph 3 PO DMF DMF
Catalyst amount (mol/mol) 0.05 0.05 0.05 0.05 0.05
TFPO conversion (%) 100 － 100 82 －
OFPO conversion (%) － 100 － － 64
244ca Selectivity (%) 99 － 98 81 －
448occc selectivity (%) － 96 － － 79
TFPO diadder selectivity (%) 0 － 0 2 －
OFPO diadder selectivity (%) － 0 － － 6
Selectivity of byproducts from TFPO (%) 1 － 2 17 －
Selectivity of byproducts from OFPO (%) － 4 － － 15
Yield of 244ca (%) 99 － 98 66 －
Yield of 448occc (%) － 96 － － 51
Example 6
A four-necked flask (reactor) equipped with a stirrer and a glass distillation column (measurement of number of plates: 5) packed with Raschig rings and a Dimu Luo Lengning reactor was immersed in an oil bath as a reaction apparatus. The reaction was carried out in the same manner as in example 1 except that a mixture of TFPO and OFPO was used as a raw material instead of TFPO, and the results are shown in table 2.
Example 7
A four-necked flask (reactor) equipped with a stirrer and a glass distillation column (measurement of number of plates: 5) packed with Raschig rings and a Dimu Luo Lengning reactor was immersed in an oil bath as a reaction apparatus. The reaction was carried out in the same manner as in example 4 except that a mixture of TFPO and OFPO was used as a raw material instead of TFPO, and the results are shown in table 2. The meaning of the sentence in table 2 is the same as that of table 1.
TABLE 2
Example 6 Example 7
Fluorine-containing alcohol TFPO,OFPO OFPO,OFPO
TFPO/OFPO(mol/mol) 1.0 1.0
Chlorinating agent SOCl 2 SOCl 2
Chlorinating dose (mol/mol) 1.1 1.1
Catalyst Ph 3 PO DMF
Catalyst amount (mol/mol) 0.05 0.05
TFPO conversion (%) 100 68
OFPO conversion (%) 100 6
244ca Selectivity (%) 98 69
448occc selectivity (%) 95 9
TFPO diadder selectivity (%) 0 12
OFPO diadder selectivity (%) 0 50
Selectivity of byproducts from TFPO (%) 2 19
Selectivity of byproducts from OFPO (%) 5 41
Yield of 244ca (%) 98 47
Yield of 448occc (%) 95 1
Example 8
Except for the use of 2-diphenylphosphorylpyridine (in the above formula (2), R 1 And R is 2 Is phenyl, R 3 Pyridyl) instead of Ph 3 The reaction was carried out in the same manner as in example 1 except that PO was used as the catalyst, and the results are shown in Table 3.
Example 9
Except that in the case of tris (4-fluorophenyl) phosphine oxide (in the above formula (2), R 1 ～R 3 All 4-fluorophenyl) instead of Ph 3 The reaction was carried out in the same manner as in example 1 except that PO was used as the catalyst, and the results are shown in Table 3. The meaning of the sentence in table 3 is the same as that of table 1.
TABLE 3
Figure BDA0004101433060000151
Industrial applicability
According to the production method of the present invention, HCFCs can be produced in high yield and high purity without reacting a fluorine-containing alcohol with a chlorinating agent in the presence of phosphine oxide by using a special operation or a reaction apparatus, and the method can be applied to mass production on an industrial scale.
The entire contents of the specification, claims, drawings and abstract of japanese patent application 2020-150467 filed on 8 months 9 in 2020 are hereby incorporated as disclosure of the specification of the present invention.

Claims (15)

1. A process for producing a hydrochlorofluorocarbon, which comprises reacting a fluorine-containing alcohol with a chlorinating agent in the presence of a catalyst to replace the hydroxyl group of the fluorine-containing alcohol with a chlorine atom,
characterized in that the catalyst is phosphine oxide,
as the chlorinating agent, at least one chlorinating agent selected from thionyl chloride, oxalyl chloride and phosgene is used.
2. The production process according to claim 1, wherein the fluorine-containing alcohol is a compound represented by the following formula (1),
X-R f -CH 2 OH(1)
wherein X represents a hydrogen atom or a fluorine atom, R f Represents a fluorinated alkylene group having 1 or more carbon atoms.
3. The manufacturing method according to claim 1 or 2, wherein, the fluorine-containing alcohol is 2,3, tetrafluoropropanol or 2,3,4, 5-octafluoropentanol.
4. The production process according to any one of claim 1 to 3, wherein the phosphine oxide is a compound represented by the following formula (2),
[ chemical 1]
Figure FDA0004101433050000011
Wherein R is 1 、R 2 、R 3 Each independently represents a monovalent hydrocarbon group which may have a substituent or a monovalent nitrogen-containing heterocyclic group which may have a substituent, wherein a carbon atom forming a ring is bonded to a phosphorus atom.
5. The method according to claim 4, wherein R is 1 ～R 3 Are all phenyl groups, or R 1 And R is 2 Is phenyl, R 3 Is pyridyl, or R 1 ～R 3 Are each 4-fluorophenyl, or R 1 ～R 3 All are 2-tolyl groups.
6. The production process according to any one of claims 1 to 5, wherein the chlorinating agent is thionyl chloride or oxalyl chloride.
7. The production method according to any one of claims 1 to 6, wherein the reaction does not contain an alcohol other than the fluorine-containing alcohol.
8. The production method according to any one of claims 1 to 7, wherein the content of the fluorine-containing alcohol adduct contained in the reaction solution obtained by the reaction is 10% by mass or less relative to the total amount of the reaction solution.
9. The production process according to any one of claims 1 to 8, wherein the reaction temperature in the reaction is 0 to 150 ℃.
10. The production method according to any one of claims 1 to 9, wherein the reaction time of the reaction is 2 to 8 hours.
11. The production process according to any one of claims 1 to 10, wherein the reaction is carried out in a molar ratio of the chlorinating agent to the fluorine-containing alcohol (chlorinating agent/fluorine-containing alcohol) of 0.01 to 100.
12. The production process according to any one of claims 1 to 11, wherein the reaction is carried out in a molar ratio of the phosphine oxide to the fluorine-containing alcohol (phosphine oxide/fluorine-containing alcohol) of 0.0001 to 10.
13. A process for producing hydrochlorofluoroolefins, characterized in that a hydrochlorofluorocarbon produced by the production process according to any one of claims 1 to 12 is subjected to dehydrofluorination in the presence of a base and/or a catalyst.
14. The manufacturing method according to claim 13, wherein, the hydrochlorofluorocarbon is 3-chloro-1, 2-tetrafluoro propane or 5-chloro-1, 2,3, 4-octafluoropentane.
15. The production process according to claim 13 or 14, wherein the hydrochlorofluoroolefin is 1-chloro-2, 3-trifluoropropene or 1-chloro-2, 3,4, 5-heptafluoropentene.
CN202180053719.XA 2020-09-08 2021-08-27 Process for producing hydrochlorofluorocarbon Pending CN115996902A (en)

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