CN111116302B - Synthesis method of halogenated butene - Google Patents
Synthesis method of halogenated butene Download PDFInfo
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- CN111116302B CN111116302B CN201911392229.3A CN201911392229A CN111116302B CN 111116302 B CN111116302 B CN 111116302B CN 201911392229 A CN201911392229 A CN 201911392229A CN 111116302 B CN111116302 B CN 111116302B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
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- 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
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX
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- C—CHEMISTRY; METALLURGY
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- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
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Abstract
The invention discloses a method for synthesizing halogenated butylene, which comprises the following steps: (1) carrying out fluorination reaction on hexachlorobutadiene and a fluorination reagent, and purifying a reaction product to obtain fluorochlorobutane; (2) and carrying out dehalogenation reaction on the chlorofluorobutane and a dehalogenation reagent in a first solvent, and purifying a reaction product to obtain the halogenated butene. The invention has the advantages of simple process, less three wastes, high yield, low cost and the like.
Description
Technical Field
The invention relates to a synthetic method of fluorohalogenated olefin, in particular to a synthetic method of halogenated butene.
Background
Fluorohalobutenes, especially hexafluorobutadiene (CF)2＝CFCF＝CF2) Because of short atmospheric service life, low greenhouse effect value and excellent environmental performance, the material has important application in the aspects of refrigerants, foaming agents, electronic special gases and the like. Such as hexafluorobutadiene, has a faster etching speed and a higher aspect ratio than those of conventional plasma etching gases, such as perfluoromethane, ethane, propane, etc., and can improve the etching stability, rate and uniformity when in use, thereby improving the quality of products.
The preparation method of the fluorohalogenated butadiene mainly comprises the following routes:
(1) fluorination of 1,2,3, 4-tetrachlorobutane fluorine gas to produce 1,2,3, 4-tetrachlorohexafluorobutane, and dechlorination of 1,2,3, 4-tetrachlorohexafluorobutane with zinc powder or the like to produce hexafluorobutadiene. The process has the advantages of large fluorine gas consumption, low fluorine gas utilization rate and easy generation of a large amount of by-products during fluorine gas phase fluorination.
For example, U.S. Pat. No. 5,430,53 reports another method for preparing hexafluorobutadiene by dehalogenation using tetrahalohexafluorobutane as an intermediate, which comprises the following steps: the gas phase fluorination reaction of 1,2,3, 4-tetrahalogenated butane and fluorine gas is carried out to generate tetrahalogenated hexafluorobutane, and then the hexafluorobutadiene is prepared by dehalogenation. The process has large fluorine gas consumption and high cost.
(2)1,2, 2-trifluoro-1, 2-dichloroiodoethane, 1, 2-tribromotrifluoroethane, 1, 4-diiodooctafluorobutane, 1-dibromotetrafluoroethane and other bromine and iodine-containing substances are used as starting materials and are subjected to coupling, dehalogenation and other reactions to generate the hexafluorobutadiene. The process has poor selectivity, and because the product does not contain bromine and iodine elements, the bromine and iodine elements are difficult to recover completely, and the lost bromine and iodine elements are finally discharged into the environment, thereby not only causing high production cost, but also causing serious environmental pollution.
For example, CN101525267 discloses a method for preparing hexafluorobutadiene from 1,2,3, 4-tetrachlorohexafluorobutane, wherein 1,2, 2-trifluoro-1, 2-dichloroiodoethane reacts with zinc particles to generate 1,2,3, 4-tetrachlorohexafluorobutane; and carrying out dehalogenation reaction on the 1,2,3, 4-tetrachlorohexafluorobutane and zinc powder in the presence of an organic solvent to generate the hexafluorobutadiene. The method uses expensive iodide, has high production cost, needs additional synthesis of the raw material 1,2, 2-trifluoro-1, 2-dichloroiodoethane, and has long process flow.
For example, US 0193643, US7504547, CN101774884 and the like react 1, 4-diiodooctafluorobutane with metal zinc in an inert solvent to remove hydrogen iodide to generate hexafluorobutadiene, and the process also has the problems of expensive raw materials, high production cost and the like.
Also for example, JP2001114710, CN102399128, CN101525267 and the like report that 1,1, 2-tribromotrifluoroethane reacts with zinc powder or magnesium powder to obtain metal organic matter of trifluorovinyl bromide, and then the metal organic matter is coupled to obtain hexafluorobutadiene. The preparation process of the 1,1, 2-tribromotrifluoroethane raw material is complex, the total flow is long, the recovery of the coupling reaction solvent is difficult, the three wastes are large, and the used bromine element causes great harm to the environment.
For example, Raghavandilai et al (J.Org.chem,2004,69: 7083-. The method has few steps and easily obtained raw materials, but the used solvent has active property and is dangerous, and the use of the solvent in large quantity is limited.
(3) Hexachlorobutadiene is used as a raw material and is subjected to four-step reactions such as catalytic hydrogenation, fluorination, chlorination, dechlorination and the like to generate the hexachlorobutadiene. The process has the problems of long route, poor selectivity of hydrodechlorination reaction, short service life of the catalyst, low total yield, difficult isomer separation and the like.
For example, CN109071374A reports a process for producing hexachlorobutadiene by catalytic hydrodechlorination of hexachlorobutadiene as a raw material to 1,2,3, 4-tetrachlorobutadiene, fluorination of 1,2,3, 4-tetrachlorobutadiene to 1,1,2,3,4, 4-hexafluoro-1, 2,3, 4-tetrachlorobutane, and dechlorination of 1,1,2,3,4, 4-hexafluoro-1, 2,3, 4-tetrachlorobutane to hexachlorobutadiene. The process has the problems of long route, poor selectivity of hydrodechlorination reaction, short service life of the catalyst, low total yield, difficult isomer separation and the like.
In a word, the existing process uses a large amount of bromine and iodine elements, the product does not contain the bromine and iodine elements, the bromine and iodine elements are difficult to recover completely, and the lost bromine and iodine elements are finally discharged into the environment, so that the production cost is high, and the serious environmental pollution is caused. By adopting the process of carrying out gas phase fluorination reaction on 1,2,3, 4-tetrahalogenated butane and fluorine gas, six molecules of fluorine gas are consumed theoretically to generate one molecule of hexafluorobutadiene, so that the consumption of fluorine gas is high, and the production cost is high.
Disclosure of Invention
Aiming at the existing defects, the invention provides the synthesis method of the halogenated butene, which has the advantages of simple process, environmental protection, high yield and low cost.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for synthesizing halogenated butene comprises the following steps:
(1) carrying out fluorination reaction on hexachlorobutadiene and a fluorination reagent, and purifying a reaction product to obtain fluorochlorobutane;
(2) and carrying out dehalogenation reaction on the chlorofluorobutane and a dehalogenation reagent in a first solvent, and purifying a reaction product to obtain the halogenated butene.
In a preferred embodiment of the present invention, the fluorinating agent is a mixed gas of fluorine and nitrogen or xenon difluoride, and the concentration of fluorine gas in the mixed gas of fluorine and nitrogen is 5 to 20 wt% (wt%, mass percentage).
In a preferred embodiment of the present invention, the fluorination reaction conditions are: the mass ratio of hexachlorobutadiene to the fluorinating agent is 1-8: 1, the reaction temperature is-80-10 ℃, and the reaction time is 4-32 h.
In a preferred embodiment of the present invention, the chlorofluorobutane is further fluorinated with a fluorinating agent and then subjected to dechlorination.
As a preferred embodiment of the present invention, the fluorinating agent is one or more of hydrogen fluoride, metal fluoride, hydrogen trifluoride triethylamine salt and quaternary ammonium fluoride salt, and the metal fluoride is preferably one or more of cesium fluoride, potassium fluoride, sodium fluoride, lithium fluoride and silver fluoride; the quaternary ammonium fluoride is preferably one or more of tetra-n-butylammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride and benzyltrimethylammonium fluoride.
In a preferred embodiment of the present invention, the conditions for the re-fluorination are: the temperature of the secondary fluorination is 50-150 ℃, the time of the secondary fluorination is 3-9 hours, and the amount of the fluorinating agent is 0.05-5 times of the mass of the hexachlorobutadiene.
As a preferred embodiment of the present invention, the fluorination reaction and the re-fluorination are carried out in a second solvent, which is one or more of 1,1, 2-trifluorotrichloroethane, perfluorotriethylamine, perfluorocyclohexane, hexafluoropropylene dimer, perfluorocyclic ether, diethylene glycol dimethyl ether, isopropanol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol methyl ether, tetraethylene glycol methyl ether, acetonitrile, propionitrile, ethyl acetate, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane; the dosage of the second solvent is 0.5-10 times of the mass of hexachlorobutadiene.
In a preferred embodiment of the present invention, the dehalogenation agent is one of powdered zinc powder, magnesium powder, copper powder, iron powder and aluminum powder.
In a preferred embodiment of the present invention, the first solvent is one or more selected from methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol methyl ether, acetonitrile, propionitrile, ethyl acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and sulfolane.
In a preferred embodiment of the present invention, the mass ratio of the dehalogenation reagent to the chlorofluorobutane is 0.1-1.0: 1, the temperature of the dehalogenation reaction is 40-80 ℃, and the reaction time is 1-5 h.
The synthesis method of the halogenated butene uses hexachlorobutadiene as a raw material and produces the halogenated butene through two reactions of fluorination and dehalogenation. The invention can produce not only hexafluorobutadiene but also fluorohaloolefins such as 1, 4-dichlorotetrafluorobutadiene, 1-chloropentafluorobutadiene and the like. The hexachlorobutadiene is a byproduct in the production process of chloroethylene, belongs to dangerous waste, and needs to be converted into harmless substances by adopting a special method.
In the present invention, hexachlorobutadiene is subjected to one-step or two-step fluorination with a fluorination reagent to produce CFxClyCFClCFClCFmClnWherein x, y, m, n are not less than 1, x + y, m + n are not less than 3, and CFCl is included2CFClCFClCFCl2、CFCl2CFClCFClCF2Cl、CF2ClCFClCFClCF2Cl, etc., CFxClyCFClCFClCFmClnDehalogenation reaction with dehalogenation reagent to obtain CFxCly-1＝CFCF＝CFmCln-1The target fluorohalobutenes of (1) include CFCl ═ CFCF ═ CFCl, CFCl ═ CFCF ═ CF2And hexafluorobutadiene CF2＝CFCF＝CF2。
The fluorinating agent for the fluorination reaction may be fluorine gas, xenon difluoride, etc., and fluorine gas is preferably selected from fluorine gas in view of cost, and the concentration of fluorine gas is preferably 1 to 20 wt%, and even higher or pure fluorine gas is possible, and the concentration of fluorine gas is preferably 5 to 20 wt% in view of process safety and production efficiency. The equivalent ratio of the fluorination reagent to hexachlorobutadiene is large, the reaction is complete, but the cost is high, and the mass ratio of hexachlorobutadiene to the fluorination reagent is preferably 1 to 8:1 from the economical viewpoint. The fluorination reaction can be carried out in the absence of a solvent, which is a compound inert under the reaction conditions, including but not limited to fluoroalkanes, fluorohaloalkanes, fluoroethers, fluoroamines, hexafluoropropylene dimers, trimers, and the like. Specifically, perfluorooctane, perfluorohexane, perfluorocyclohexane, perfluoromethylcyclohexane, trifluorotrichloroethane, difluorotetrachloroethane, perfluorocyclic ether, perfluorotri-n-butylamine, hexafluoropropylene dimer, trimer, etc. The amount of the solvent is preferably 0.5-10 times of the mass of hexachlorobutadiene, and a higher amount of the solvent is feasible, and the current amount is selected for economic reasons. The reaction temperature is low, the selectivity is high, but the lower temperature corresponds to higher energy consumption, and the reaction temperature is-80-10 ℃, preferably-60-0 ℃ from the aspects of economy and operability.
The fluorinating agent for the secondary fluorination reaction can be one or more of hydrogen fluoride, metal fluoride, hydrogen trifluoride triethylamine salt, quaternary ammonium fluoride and quaternary phosphonium fluoride, and the metal fluoride can be cesium fluoride, potassium fluoride, sodium fluoride, lithium fluoride, silver fluoride and the like. The quaternary ammonium fluoride salt and the quaternary phosphonium fluoride salt are tetra-n-butylammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, benzyltrimethylammonium fluoride and the like. When hydrogen fluoride and metal fluoride are used as fluorinating agent, certain amount of catalyst such as antimony pentachloride, titanium tetrachloride, quaternary ammonium salt, quaternary phosphonium salt, crown ether, etc. can be added. The quaternary ammonium fluoride salt and the quaternary phosphonium fluoride salt have high activity, the selectivity of triethylamine hydrogen trifluoride salt and silver fluoride is high, the equivalent ratio of a fluorination reagent to a reactant to be fluorinated is large, the reaction is complete, a certain over-fluorinated byproduct exists, and the usage amount of the fluorination reagent is preferably 0.05-5 times of the mass of hexachlorobutadiene from the aspects of economy and selectivity. The solvent can be alcohol, ether, nitrile, ester and polar solvent containing nitrogen and sulfur atoms, specifically ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol methyl ether, tetraethylene glycol methyl ether, acetonitrile, propionitrile, ethyl acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, etc. In view of economy and reaction rate, the amount of the solvent used is preferably 0.5 to 10 times, more preferably 1 to 4 times, the mass of hexachlorobutadiene. The reaction temperature is high, the reaction speed is high, the number of over-fluorinated byproducts is increased, the reaction temperature is low, the number of over-fluorinated byproducts can be reduced, the selectivity is improved, and the reaction temperature can be 40-150 ℃, preferably 60-120 ℃; the reaction pressure is mainly the vapor pressure of the materials at the reaction temperature, and can be carried out under the conditions of normal pressure and higher than normal pressure.
As the dehalogenating agent, powdery zinc, magnesium, copper, iron, aluminum and the like can be used, and zinc and magnesium are preferable from the viewpoint of reaction results. The dehalogenation solvent is one or more of alcohol, ether, nitrile and polar solvent containing nitrogen and sulfur atoms, specifically methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol methyl ether, tetraethylene glycol methyl ether, acetonitrile, propionitrile, ethyl acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and the like, and the dehalogenation solvent is preferably one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol methyl ether, acetonitrile, propionitrile, ethyl acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and sulfolane.
Compared with the prior art, the invention has the advantages that:
1. the process is simple, and the synthesis process of halogenated butene has obviously simplified process, and the process adopts hexachlorobutadiene as material and produces halogenated butene through two reactions of fluorination and dehalogenation.
2. The method is green and environment-friendly, hexachlorobutadiene is a byproduct in the production process of chloroethylene, belongs to dangerous waste, and needs to be converted into harmless substances by adopting a special method, so that not only are industrial byproducts converted into high-value products, but also the consumption of fluorine gas is reduced, and theoretically, only two molecules of fluorine gas are consumed for producing one molecule of hexachlorobutadiene;
3. the raw materials are cheap and easy to obtain, the cost is low, hexachlorobutadiene is a byproduct in the production process of chloroethylene, and is cheap and easy to obtain;
4. the method has high operation flexibility and is easy to industrialize, and the method can be used for producing not only the hexafluorobutadiene but also fluorohaloolefins such as 1, 4-dichlorotetrafluorobutadiene, 1-chloropentafluorobutadiene and the like.
Detailed Description
Aiming at the existing defects, the invention provides the synthesis method of the halogenated butene, which has the advantages of simple process, environmental protection, high yield and low cost.
In order to realize the purpose, the invention adopts the technical scheme that: a method for synthesizing halogenated butene comprises the following steps:
(1) carrying out fluorination reaction on hexachlorobutadiene and a fluorination reagent, and purifying a reaction product to obtain fluorochlorobutane;
(2) and carrying out dehalogenation reaction on the chlorofluorobutane and a dehalogenation reagent in a first solvent, and purifying a reaction product to obtain the halogenated butene.
In a preferred embodiment of the present invention, the fluorinating agent is a mixed gas of fluorine and nitrogen or xenon difluoride, and the concentration of fluorine gas in the mixed gas of fluorine and nitrogen is 5 to 20 wt% (wt%, mass percentage).
In a preferred embodiment of the present invention, the fluorination reaction conditions are: the mass ratio of hexachlorobutadiene to the fluorinating agent is 1-8: 1, the reaction temperature is-80-10 ℃, and the reaction time is 4-32 h.
In a preferred embodiment of the present invention, the chlorofluorobutane is further fluorinated with a fluorinating agent and then subjected to dechlorination.
As a preferred embodiment of the present invention, the fluorinating agent is one or more of hydrogen fluoride, metal fluoride, hydrogen trifluoride triethylamine salt and quaternary ammonium fluoride salt, and the metal fluoride is preferably one or more of cesium fluoride, potassium fluoride, sodium fluoride, lithium fluoride and silver fluoride; the quaternary ammonium fluoride is preferably one or more of tetra-n-butylammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride and benzyltrimethylammonium fluoride.
In a preferred embodiment of the present invention, the conditions for the re-fluorination are: the re-fluorination temperature is 50-150 ℃, the re-fluorination time is 3-9 hours, and the consumption of the fluorinating agent is 0.05-5 times of the mass of hexachlorobutadiene.
As a preferred embodiment of the present invention, the fluorination reaction and the re-fluorination are carried out in a second solvent, which is one or more of 1,1, 2-trifluorotrichloroethane, perfluorotriethylamine, perfluorocyclohexane, hexafluoropropylene dimer, perfluorocyclic ether, diethylene glycol dimethyl ether, isopropanol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol methyl ether, tetraethylene glycol methyl ether, acetonitrile, propionitrile, ethyl acetate, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane; the dosage of the second solvent is 0.5-10 times of the mass of the hexachlorobutadiene.
In a preferred embodiment of the present invention, the dehalogenation agent is one of powdered zinc powder, magnesium powder, copper powder, iron powder and aluminum powder.
In a preferred embodiment of the present invention, the first solvent is one or more selected from methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol methyl ether, acetonitrile, propionitrile, ethyl acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and sulfolane.
In a preferred embodiment of the present invention, the mass ratio of the dehalogenation reagent to the chlorofluorobutane is 0.1-1.0: 1, the temperature of the dehalogenation reaction is 40-80 ℃, and the reaction time is 1-5 h.
The synthesis method of the halogenated butene uses hexachlorobutadiene as a raw material and produces the halogenated butene through two reactions of fluorination and dehalogenation. The invention can produce not only hexafluorobutadiene but also fluorohaloolefins such as 1, 4-dichlorotetrafluorobutadiene, 1-chloropentafluorobutadiene and the like. The hexachlorobutadiene is a byproduct in the production process of chloroethylene, belongs to dangerous waste, and needs to be converted into harmless substances by adopting a special method.
In the present invention, hexachlorobutadiene is subjected to one-step or two-step fluorination with a fluorination reagent to produce CFxClyCFClCFClCFmClnWherein x, y, m, n are not less than 1, x + y, m + n are not less than 3, and CFCl is included2CFClCFClCFCl2、CFCl2CFClCFClCF2Cl、CF2ClCFClCFClCF2Cl, etc., CFxClyCFClCFClCFmClnDehalogenation reaction with dehalogenation reagent to obtain CFxCly-1＝CFCF＝CFmCln-1The target fluorohalobutenes of (1) include CFCl ═ CFCF ═ CFCl, CFCl ═ CFCF ═ CF2And hexafluorobutadiene CF2＝CFCF＝CF2。
The fluorinating agent for the fluorination reaction may be fluorine gas, xenon difluoride, etc., and fluorine gas is preferably selected from fluorine gas in view of cost, and the concentration of fluorine gas is preferably 1 to 20 wt%, and even higher or pure fluorine gas is possible, and the concentration of fluorine gas is preferably 5 to 20 wt% in view of process safety and production efficiency. The equivalent ratio of the fluorination reagent to hexachlorobutadiene is large, the reaction is complete, but the cost is high, and the mass ratio of hexachlorobutadiene to the fluorination reagent is preferably 1 to 8:1 from the economical viewpoint. The fluorination reaction can be carried out in the absence of a solvent, which is a compound inert under the reaction conditions, including but not limited to fluoroalkanes, fluorohaloalkanes, fluoroethers, fluoroamines, hexafluoropropylene dimers, trimers, and the like. Specifically, perfluorooctane, perfluorohexane, perfluorocyclohexane, perfluoromethylcyclohexane, trifluorotrichloroethane, difluorotetrachloroethane, perfluorocyclic ether, perfluorotri-n-butylamine, hexafluoropropylene dimer, trimer, etc. The amount of the solvent is preferably 0.5 to 10 times of the mass of hexachlorobutadiene, and a higher amount of the solvent is feasible, and the current amount is selected for economic reasons. The reaction temperature is low, the selectivity is high, but the lower temperature corresponds to higher energy consumption, and the reaction temperature is-80-10 ℃, preferably-60-0 ℃ from the aspects of economy and operability.
The fluorinating agent for the secondary fluorination reaction can be one or more of hydrogen fluoride, metal fluoride, hydrogen trifluoride triethylamine salt, quaternary ammonium fluoride and quaternary phosphonium fluoride, and the metal fluoride can be cesium fluoride, potassium fluoride, sodium fluoride, lithium fluoride, silver fluoride and the like. The quaternary ammonium fluoride salt and the quaternary phosphonium fluoride salt are tetra-n-butylammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, benzyltrimethylammonium fluoride and the like. When hydrogen fluoride and metal fluoride are used as fluorinating agent, certain amount of catalyst such as antimony pentachloride, titanium tetrachloride, quaternary ammonium salt, quaternary phosphonium salt, crown ether, etc. can be added. The quaternary ammonium fluoride salt and the quaternary phosphonium fluoride salt have high activity, the selectivity of triethylamine hydrogen trifluoride salt and silver fluoride is high, the equivalent ratio of a fluorination reagent to a reactant to be fluorinated is large, the reaction is complete, a certain over-fluorinated byproduct exists, and the usage amount of the fluorination reagent is preferably 0.05-5 times of the mass of hexachlorobutadiene from the aspects of economy and selectivity. The solvent can be alcohol, ether, nitrile, ester and polar solvent containing nitrogen and sulfur atoms, specifically ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol methyl ether, tetraethylene glycol methyl ether, acetonitrile, propionitrile, ethyl acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, etc. In view of economy and reaction rate, the amount of the solvent used is preferably 0.5 to 10 times, more preferably 1 to 4 times, the mass of hexachlorobutadiene. The reaction temperature is high, the reaction speed is high, the number of over-fluorinated byproducts is increased, the reaction temperature is low, the number of over-fluorinated byproducts can be reduced, the selectivity is improved, and the reaction temperature can be 40-150 ℃, preferably 60-120 ℃; the reaction pressure is mainly the vapor pressure of the materials at the reaction temperature, and can be carried out under the conditions of normal pressure and higher than normal pressure.
As the dehalogenating agent, powdery zinc, magnesium, copper, iron, aluminum and the like can be used, and zinc and magnesium are preferable from the viewpoint of reaction results. The dehalogenation solvent is one or more of alcohol, ether, nitrile and polar solvent containing nitrogen and sulfur atoms, specifically methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol methyl ether, tetraethylene glycol methyl ether, acetonitrile, propionitrile, ethyl acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and the like, and the dehalogenation solvent is preferably one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol methyl ether, acetonitrile, propionitrile, ethyl acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and sulfolane.
Compared with the prior art, the invention has the advantages that:
5. the method for synthesizing the halogenated butene takes hexachlorobutadiene as a raw material and produces the halogenated butene through two reactions of fluorination and dehalogenation, thereby obviously simplifying the process.
6. The method is green and environment-friendly, hexachlorobutadiene is a byproduct in the production process of chloroethylene, belongs to dangerous waste, and needs to be converted into harmless substances by adopting a special method, so that not only are industrial byproducts converted into high-value products, but also the consumption of fluorine gas is reduced, and theoretically, only two molecules of fluorine gas are consumed for producing one molecule of hexachlorobutadiene;
7. the raw materials are cheap and easy to obtain, the cost is low, hexachlorobutadiene is a byproduct in the production process of chloroethylene, and is cheap and easy to obtain;
8. the method has high operation flexibility and is easy to industrialize, and the method can be used for producing not only the hexafluorobutadiene but also fluorohaloolefins such as 1, 4-dichlorotetrafluorobutadiene, 1-chloropentafluorobutadiene and the like.
Example 1
(1) Fluorination of
Adding 1000g of 1,1, 2-trifluorotrichloroethane and 522g of hexachlorobutadiene into a 2L pressure reaction kettle, stirring, cooling the reaction kettle to-60 ℃, introducing 20 wt% of fluorine-nitrogen mixed gas at the flow rate of 200g/h, stopping introducing the fluorine-nitrogen mixed gas after 5h, and introducing the fluorine-nitrogen mixed gas
50g/h of nitrogen is added for 1h, the reaction kettle is heated to room temperature, the material is discharged, and the 1,2,3, 4-tetrafluorohexachlorobutane with the purity of 99.5 percent is obtained after rectification, and the yield is 82 percent.
(2) Dechlorination
Adding 200g of methanol and 33g of zinc powder into a 1L four-neck flask with a reflux condenser, a dropping funnel and mechanical stirring, heating to 65 ℃, adding 84g of 1,2,3, 4-tetrafluorohexachlorobutane obtained by the method in the step (1) in 1h, continuing to react for 1h after dropwise addition, cooling, filtering and rectifying to obtain 1, 4-dichlorotetrafluorobutadiene with the purity of 99.2 percent, wherein the yield is 91 percent.
Example 2
(1) Fluorination of
Adding 1000g of perfluorocyclohexane and 131g of hexachlorobutadiene into a 2L pressure reaction kettle, stirring, cooling the reaction kettle to 0 ℃, introducing 20 wt% of fluorine-nitrogen mixed gas at the flow rate of 100g/h, stopping introducing the fluorine-nitrogen mixed gas after 4h, introducing 50g/h of nitrogen for 2h, heating the reaction kettle to room temperature, discharging, and rectifying to obtain the 1,2,3, 4-tetrafluorohexachlorobutane with the purity of 99.5%, wherein the yield is 76%.
(2) Is once again fluorinated
304g of 1,2,3, 4-tetrafluorohexachlorobutane obtained by the method in the step (1) and 644g of triethylamine trifluoride are added into a 2L pressure reaction kettle, stirred, heated to 100 ℃, reacted for 8 hours, cooled, washed by water and rectified to obtain 1,1,2,3,4, 4-hexafluorotetrachlorobutane with the purity of 99.1 percent, and the yield is 85 percent.
(3) Dechlorination
160g of isopropanol and 79g of zinc powder are added into a 1L four-neck flask with a reflux condenser, a dropping funnel and mechanical stirring, the outlet of the reflux condenser is connected with a cold trap at the temperature of-20 ℃, the stirring is carried out, the temperature is raised to 60 ℃, 152g of 1,1,2,3,4, 4-hexafluorotetrachlorobutane obtained by the method in the step (2) is added within 2h, the reaction is continued for 2h after the dropwise addition is finished, the crude product of the hexafluorobutadiene is distilled out, the crude product is rectified to obtain the hexafluorobutadiene with the purity of 99.9 percent, and the yield is 93 percent.
Example 3
(1) Fluorination of
1044g of hexachlorobutanedioic acid are added into a 2L pressure reaction kettle
And (2) stirring, cooling the reaction kettle to-15 ℃, introducing 5 wt% of fluorine-nitrogen mixed gas at the flow rate of 200g/h, stopping introducing the fluorine-nitrogen mixed gas after 32h, introducing 50g/h of nitrogen for 1.2h, heating the reaction kettle to room temperature, discharging, and rectifying to obtain the 1,2,3, 4-tetrafluorohexachlorobutane with the purity of 99.0%, wherein the yield is 72%.
(2) Is once again fluorinated
Adding 85g of hydrogen fluoride, 608g of 1,2,3, 4-tetrafluorohexachlorobutane obtained by the method in the step (1) and 10g of antimony pentachloride into a 2L pressure reaction kettle, stirring, heating the reaction kettle to 70 ℃, reacting for 4 hours, cooling, washing with water, and rectifying to obtain the 1,1,2,3,4, 4-hexafluorotetrachlorobutane with the purity of 98.5 percent, wherein the yield is 84 percent.
(3) Dechlorination
Adding 240g of diethylene glycol dimethyl ether and 42.5g of zinc powder into a 1L four-neck flask with a reflux condenser, a dropping funnel and mechanical stirring, connecting an outlet of the reflux condenser with a cold trap at the temperature of-20 ℃, stirring, heating to 80 ℃, adding 76g of 1,1,2,3,4, 4-hexafluorotetrachlorobutane obtained by the method in the step (2) within 1.2h, continuing to react for 3h after dropwise addition is finished, distilling a crude product of the hexafluorobutadiene, and rectifying to obtain the hexafluorobutadiene with the purity of 99.5%, wherein the yield is 75%.
Example 4
(1) Fluorination of
Adding 500g of hexafluoropropylene dimer and 522g of hexachlorobutadiene into a 2L pressure reaction kettle, stirring, cooling the reaction kettle to-30 ℃, introducing 5 wt% of fluorine-nitrogen mixed gas at the flow rate of 200g/h, stopping introducing the fluorine-nitrogen mixed gas after 18h,
50g/h of nitrogen is added for 2h, the reaction kettle is heated to room temperature, the material is discharged, and the 1,2,3, 4-tetrafluorohexachlorobutane with the purity of 99.2 percent is obtained after rectification, and the yield is 85 percent.
(2) Is once again fluorinated
300g of diethylene glycol dimethyl ether, 152g of 1,2,3, 4-tetrafluorohexachlorobutane obtained by the method in the step (1) and 150g of tetramethylammonium fluoride are added into a 1L four-neck flask, stirred, heated to 80 ℃ in a reaction kettle, reacted for 6 hours, cooled, washed by water and rectified to obtain 1,1,2,3,4, 4-hexafluorotetrachlorobutane with the purity of 99.5 percent, and the yield is 87 percent.
(3) Dechlorination
Adding 240g of ethanol and 36g of zinc powder into a 1L four-neck flask with a reflux condenser, a dropping funnel and mechanical stirring, connecting an outlet of the reflux condenser with a cold trap at the temperature of-20 ℃, stirring, heating to 80 ℃, adding 76g of 1,1,2,3,4, 4-hexafluorotetrachlorobutane obtained by the method in the step (2) into the flask within 2h, continuing to react for 3h after dropwise addition is finished, evaporating out a crude product of hexafluorobutadiene, and rectifying the crude product to obtain the hexafluorobutadiene with the purity of 99.5%, wherein the yield is 95%.
Example 5
(1) Fluorination of
Adding 1000g of perfluorinated triethylamine, 30g of potassium fluoride and 261g of hexachlorobutadiene into a 2L pressure reaction kettle, stirring, cooling the reaction kettle to-30 ℃, introducing a fluorine-nitrogen mixed gas with the concentration of 10 wt% at the flow rate of 200g/h, stopping introducing the fluorine-nitrogen mixed gas after 5h, introducing 50g/h of nitrogen for 1.5h, heating the reaction kettle to 120 ℃, and reacting
Cooling, washing and rectifying for 4h to obtain the 1,1,2,3, 4-pentafluoropentachlorobutane with the purity of 98.6 percent and the yield of 60 percent.
(2) Dechlorination
Adding 300g of N, N-dimethylformamide and 49g of zinc powder into a 1L four-neck flask with a reflux condenser, a dropping funnel and mechanical stirring, connecting an outlet of the reflux condenser with a cold trap at the temperature of-20 ℃, stirring, heating to 40 ℃, adding 80g of 1,1,2,3, 4-pentafluoropentachlorobutane obtained by the method in the step (1) into the flask within 1.5h, continuing to react for 1h after dropwise addition, cooling the reaction solution, filtering, distilling to obtain a 1-chloropentafluorobutadiene crude product, and rectifying the crude product to obtain the 1-chloropentafluorobutadiene with the purity of 99.3 percent, wherein the yield is 87 percent.
Example 6
(1) Fluorination of
1000g of perfluorocyclic ether was added to a 2L pressure reactor
80g of potassium fluoride and 261g of hexachlorobutadiene, stirring, cooling the reaction kettle to-30 ℃, introducing a fluorine-nitrogen mixed gas with the concentration of 10 wt% at the flow rate of 200g/h, stopping introducing the fluorine-nitrogen mixed gas after 5h, introducing 50g/h of nitrogen for 1.5h, heating the reaction kettle to 120 ℃, reacting for 6h, cooling, washing with water, and rectifying to obtain 1,1,2,3,4, 4-hexafluorotetrachlorobutane with the purity of 99.5%, wherein the yield is 80%.
(2) Dechlorination
300g of N, N-dimethylformamide and 49g of zinc powder are added into a 1L four-neck flask with a reflux condenser, a dropping funnel and mechanical stirring, the outlet of the reflux condenser is connected with a cold trap at the temperature of-20 ℃, the stirring is carried out, the temperature is raised to 60 ℃, 76g of 1,1,2,3,4, 4-hexafluorotetrachlorobutane obtained by the method in the step (1) is added within 1.5h, the reaction is continued for 1h after the dropwise addition is finished, the reaction solution is cooled, the filtration is carried out, the crude hexafluorobutadiene product is obtained by distillation, the crude hexafluorobutadiene product is rectified to obtain the hexafluorobutadiene product with the purity of 99.5 percent, and the yield is 95 percent.
Claims (4)
1. A method for synthesizing halogenated butene is characterized by comprising the following steps:
(1) carrying out fluorination reaction on hexachlorobutadiene and a fluorination reagent in a reaction kettle, wherein the fluorination reagent is a fluorine-nitrogen mixed gas, and the conditions of the fluorination reaction are as follows: the mass ratio of hexachlorobutadiene to the fluorinating agent is 1-8: 1, the reaction temperature is-80-10 ℃, the reaction time is 4-32 hours, and the reaction product is purified to obtain chlorofluorobutane;
(2) fluorinating the fluorochlorobutane again by using a fluorinating agent, wherein the fluorinating agent is one or more of metal fluoride, hydrogen trifluoride triethylamine salt and quaternary ammonium fluoride salt, and the metal fluoride is one or more of cesium fluoride, potassium fluoride, sodium fluoride, lithium fluoride and silver fluoride; the quaternary ammonium fluoride is one or more of tetra-n-butylammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride and benzyl trimethyl ammonium fluoride;
(3) carrying out dehalogenation reaction on the fluorochlorobutane after re-fluorination and a dehalogenation reagent in a first solvent at the temperature of 40-80 ℃ for 1-5 h, purifying the reaction product to obtain halogenated butene, wherein the mass ratio of the dehalogenation reagent to the fluorochlorobutane is 0.1-1.0: 1, the dehalogenation reagent is powdered zinc powder, and the first solvent is one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol methyl ether, acetonitrile, propionitrile, ethyl acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and sulfolane.
2. The method for synthesizing halogenated butene according to claim 1, wherein the concentration of fluorine gas in the mixed gas of fluorine and nitrogen is 5 to 20% by weight.
3. The process for the synthesis of halogenated butenes according to claim 1, characterized in that the conditions for the re-fluorination are: the temperature of the secondary fluorination is 50-150 ℃, the time of the secondary fluorination is 3-9 hours, and the amount of the fluorinating agent is 0.05-5 times of the mass of the hexachlorobutadiene.
4. The method of synthesizing halogenated butene according to claim 1, wherein the re-fluorination is carried out in a second solvent which is one or more of 1,1, 2-trifluorotrichloroethane, perfluorotriethylamine, perfluorocyclohexane, hexafluoropropylene dimer, perfluorocyclic ether, diethylene glycol dimethyl ether, isopropanol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol methyl ether, tetraethylene glycol methyl ether, acetonitrile, propionitrile, ethyl acetate, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane; the dosage of the second solvent is 0.5-10 times of the mass of hexachlorobutadiene.
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| CN107667085A (en) * | 2015-06-04 | 2018-02-06 | 索尔维特殊聚合物意大利有限公司 | Method for synthesizing 1,2,3,4 tetrachloro-hexafluoro butanes |
| CN109071384A (en) * | 2016-04-04 | 2018-12-21 | 阿科玛法国公司 | The method for preparing hexachlorobutadiene |
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| CN103193586A (en) * | 2013-03-14 | 2013-07-10 | 巨化集团技术中心 | Synthetic method of 1,1,1,4,4,4-hexafluoro-2-butene |
| CN107667085A (en) * | 2015-06-04 | 2018-02-06 | 索尔维特殊聚合物意大利有限公司 | Method for synthesizing 1,2,3,4 tetrachloro-hexafluoro butanes |
| CN109071384A (en) * | 2016-04-04 | 2018-12-21 | 阿科玛法国公司 | The method for preparing hexachlorobutadiene |
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| The Research Progress of Hexafluorobutadiene Synthesis;Jing Zhu et al.;《International Journal of Organic Chemistry》;20141231;第4卷;第331-338页 * |
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