CN113004118A - Method for preparing hexafluorobutadiene by using high-boiling point strong-polarity solvent - Google Patents
Method for preparing hexafluorobutadiene by using high-boiling point strong-polarity solvent Download PDFInfo
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- CN113004118A CN113004118A CN202110177453.1A CN202110177453A CN113004118A CN 113004118 A CN113004118 A CN 113004118A CN 202110177453 A CN202110177453 A CN 202110177453A CN 113004118 A CN113004118 A CN 113004118A
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- tetrachlorohexafluorobutane
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention relates to a method for preparing hexafluorobutadiene by using a high-boiling point strong-polarity solvent, belonging to the technical field of organic chemical preparation; the method comprises the following steps: mixing zinc powder and a high-boiling point strong polar solvent, stirring, dropwise adding 1,2,3, 4-tetrachlorohexafluorobutane into the mixture for reaction when the temperature is 50-70 ℃, reacting for 1-2 h after dropwise adding 1,2,3, 4-tetrachlorohexafluorobutane to obtain a reaction product, drying the product, collecting the product in a cold trap, and collecting the collected gas, namely, the hexafluorobutadiene; the high boiling point strong polar solvent is a solvent with a boiling point of more than 180 ℃ and a polarity of more than 5.0; the mass ratio of the zinc powder to the 1,2,3, 4-tetrachlorohexafluorobutane is 2:1 to 5: 1; the cold trap collection temperature is-50-6 ℃; the method has low energy consumption and relatively mild reaction conditions.
Description
Technical Field
The invention relates to a method for preparing hexafluorobutadiene by using a high-boiling point strong-polarity solvent, belonging to the technical field of organic chemical preparation.
Background
Hexafluorobutadiene is an excellent dry etching agent as a perfluorinated compound having two double bonds. In recent years, hexafluorobutadiene has been increasingly used in dry etching of very large scale integrated circuits. There are many methods for producing hexafluorobutadiene, and among them, there is a method of reacting 1,2,3, 4-tetrachlorohexafluorobutane with zinc powder as a raw material in a solvent such as ethanol, isopropanol, a nonpolar substance, dioxane, or the like; the solvent commonly used in the reaction is isopropanol, in addition, U.S. Pat. No. 3, 2894042A discloses that ethanol is used as the solvent for the reaction, and patent WO2005023734A1 discloses that 1,2,3, 4-tetrachlorohexafluorobutane and zinc powder are subjected to dechlorination reaction in dioxane solvent under the protection of nitrogen to generate hexafluorobutadiene.
Wherein, the ethanol, isopropanol or dioxane is adopted as the solvent, and the following defects exist: the boiling points of ethanol, isopropanol and dioxane are low, when the three substances are used as solvents, the three substances can boil in the reaction process, and a small amount of solvent enters a collecting cold trap along with the hexafluorobutadiene, so that the purity of the hexafluorobutadiene is not high, and the subsequent separation and purification are influenced; in addition, the vaporization of the solvent can cause the dispersion of zinc powder in the solvent, thereby influencing the yield of the hexafluorobutadiene; in addition, the boiling of the solvent also needs a cooler to cool and reflux the solvent, thus improving the energy consumption of the reaction.
The use of non-polar materials as solvents has the following disadvantages: the reaction temperature required by the method is higher, so that the energy consumption is high; and the solubility of zinc chloride generated by the reaction in nonpolar substances is low, and the reaction of zinc powder is incomplete, so that the yield of the hexafluorobutadiene is reduced.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing hexafluorobutadiene by using a high-boiling point and strong polar solvent, wherein the method is low in energy consumption and relatively mild in reaction conditions.
In order to achieve the purpose of the invention, the following technical scheme is provided.
A method for preparing hexafluorobutadiene by using a high-boiling point strong polar solvent comprises the following steps:
mixing zinc powder and a high-boiling point strong polar solvent, stirring, dropwise adding 1,2,3, 4-tetrachlorohexafluorobutane into the mixture for reaction when the temperature is 50-70 ℃, reacting for 1-2 h after dropwise adding 1,2,3, 4-tetrachlorohexafluorobutane to obtain a reaction product, drying the product, collecting the product in a cold trap, and collecting the collected gas, namely the hexafluorobutadiene.
Wherein the high boiling point strong polar solvent is a solvent with a boiling point of more than 180 ℃ and a polarity of more than 5.0.
The ratio of the zinc powder to the 1,2,3, 4-tetrachlorohexafluorobutane is 2:1 to 5: 1.
The cold trap collection temperature is-50-6 ℃.
Preferably, the high-boiling point strongly polar solvent is dimethyl sulfoxide (DMSO), ethylene glycol or N-methylpyrrolidone (NMP).
Preferably, 1,2,3, 4-tetrachlorohexafluorobutane is added in one drop at a rate of 2 seconds.
Preferably, zeolite, phosphorus pentoxide, calcium chloride or concentrated sulfuric acid with the mass fraction of 98% can be used as the drying agent.
Advantageous effects
(1) The method for preparing the hexafluorobutadiene by using the high-boiling point strong polar solvent selects the high-boiling point strong polar solvent as the reaction solvent, and the solvent does not boil under the reaction condition of 50-70 ℃, so that the solvent and the generated hexafluorobutadiene are prevented from entering a collecting cold trap together, the yield of the hexafluorobutadiene is improved, and the subsequent separation and purification are facilitated, so that the higher-purity hexafluorobutadiene is obtained.
Meanwhile, the polarity of the selected solvent is more than 5.0, so that the solubility of zinc chloride generated in the reaction process in the polar solvent is high, the zinc powder is reacted completely, and the yield of the hexafluorobutadiene is improved.
(2) The method adopts the high-boiling point strong polar solvent to replace the low-boiling point solvent, reduces the volatilization of the solvent in the reaction process, avoids the use of a solvent cooler and reduces the energy consumption.
(3) The method adopts the high-boiling point strong-polarity solvent as the reaction solvent, so that the method has the advantages of lower reaction temperature, mild reaction condition and low energy consumption.
(4) The method provided by the invention is used for drying the generated hexafluorobutadiene gas, so that the phenomenon that the pipeline is blocked by moisture in the cold trap collection process is prevented.
Detailed Description
The invention will be described in more detail with reference to specific examples, which should not be construed as limiting the scope of the invention.
In the following examples:
the end products of the examples and comparative examples were subjected to test analysis by gas chromatography under the following test conditions: maintaining the temperature of the chromatographic vaporizer at 150 deg.C and 250 deg.C for 8min, and maintaining the temperature at 20 deg.C/min to 170 deg.C and maintaining the temperature for 20 min; the hexafluorobutadiene retention time was 5.9 minutes.
Example 1
A method for preparing hexafluorobutadiene by using a high-boiling point strong polar solvent comprises the following steps:
26.0g of zinc powder is added into 50mL of ethylene glycol to be mixed, stirred, the reaction temperature is set to be 50 ℃, then 1,2,3, 4-tetrachlorohexafluorobutane is dripped into the zinc powder to react, wherein the mass of the 1,2,3, 4-tetrachlorohexafluorobutane is 30.4g, the dripping speed of the 1,2,3, 4-tetrachlorohexafluorobutane is 2 seconds, after 1,2,3, 4-tetrachlorohexafluorobutane is dripped, the reaction is carried out for 2 hours to obtain a reaction product, the product is dried by a drier filled with phosphorus pentoxide, and finally the product is collected in a cold trap at the temperature of-20 ℃ to obtain a final product, the mass of the final product is 13.4g, and the final product is tested by gas chromatography to know that the final product contains hexafluorobutadiene, the purity of the hexafluorobutadiene is 97.5%, and the yield of the hexafluorobutadiene is 80.9%.
Example 2
A method for preparing hexafluorobutadiene by using a high-boiling point strong polar solvent comprises the following steps:
26.0g of zinc powder is added into 50mL of ethylene glycol to be mixed, stirred, the reaction temperature is set to be 50 ℃, then 1,2,3, 4-tetrachlorohexafluorobutane is dropwise added into the mixture to react, wherein the mass of the 1,2,3, 4-tetrachlorohexafluorobutane is 30.4g, after the 1,2,3, 4-tetrachlorohexafluorobutane is dropwise added, the reaction is carried out for 2 hours to obtain a reaction product, the product is dried by a dryer filled with zeolite, and finally the product is collected in a cold trap at the temperature of-20 ℃ to obtain a final product with the mass of 12.9g, and the final product is tested by gas chromatography, so that the final product contains hexafluorobutadiene, the purity of the hexafluorobutadiene is 95.8%, and the yield of the hexafluorobutadiene is 76.7%.
Example 3
A method for preparing hexafluorobutadiene by using a high-boiling point strong polar solvent comprises the following steps:
19.5g of zinc powder is added into 50mL of DMSO for mixing, stirring is carried out, the reaction temperature is set to be 60 ℃, then 1,2,3, 4-tetrachlorohexafluorobutane is dropwise added into the DMSO for reaction, wherein the mass of the 1,2,3, 4-tetrachlorohexafluorobutane is 30.4g, the dropping speed of the 1,2,3, 4-tetrachlorohexafluorobutane is one drop per 2 seconds, after 1,2,3, 4-tetrachlorohexafluorobutane is dropwise added, the reaction is carried out for 2 hours to obtain a reaction product, the reaction product is dried by a drier filled with calcium chloride, and finally the reaction product is collected in a cold trap at the temperature of-25 ℃ to obtain a final product, the mass of the final product is 12.7g, and the final product is tested by gas chromatography to know that the purity of the hexafluorobutadiene is 92.1%, and the yield of the hexafluorobutadiene is 72.4%.
Example 4
A method for preparing hexafluorobutadiene by using a high-boiling point strong polar solvent comprises the following steps:
adding 32.5g of zinc powder into 50mL of NMP, mixing, stirring, setting the reaction temperature to 65 ℃, then dropwise adding 1,2,3, 4-tetrachlorohexafluorobutane into the mixture to react, wherein the mass of the 1,2,3, 4-tetrachlorohexafluorobutane is 30.4g, the dropwise adding speed of the 1,2,3, 4-tetrachlorohexafluorobutane is one drop per 2 seconds, after the 1,2,3, 4-tetrachlorohexafluorobutane is dropwise added, reacting for 1 hour to obtain a reaction product, drying the product by a dryer filled with concentrated sulfuric acid with the mass fraction of 98%, and finally collecting the product in a cold trap with the temperature of-30 ℃ to obtain a final product, wherein the mass of the final product is 12.0g, and the gas chromatography test shows that the final product contains hexafluorobutadiene, the purity of the hexafluorobutadiene is 90.0%, and the yield of the hexafluorobutadiene is 66.8%.
Comparative example 1
26.0g of zinc powder is added into 50mL of isopropanol and mixed, the mixture is stirred, the reaction temperature is set to be 80 ℃, then 1,2,3, 4-tetrachlorohexafluorobutane is dropwise added into the mixture for reaction, wherein the mass of the 1,2,3, 4-tetrachlorohexafluorobutane is 30.4g, the dropping speed of the 1,2,3, 4-tetrachlorohexafluorobutane is one drop per 2 seconds, after 1,2,3, 4-tetrachlorohexafluorobutane is dropwise added, the reaction is carried out for 2 hours, a reaction product is obtained, the product is dried by a drier filled with phosphorus pentoxide, and finally the product enters a cold trap at the temperature of-20 ℃ for collection, a final product is obtained, the mass of the final product is 14.7g, and the gas chromatography test shows that the final product contains hexafluorobutadiene, the purity of the hexafluorobutadiene is 71.7%, and the yield of the hexafluorobutadiene is 64.9%.
Some of the conditions and yields for the preparation of hexafluorobutadiene in examples 1 to 4 and comparative example 1 were collated and are shown in Table 1:
TABLE 1 partial conditions and yields for preparation of hexafluorobutadiene in examples 1-4 and comparative example 1
As can be seen from Table 1, in comparative example 1, isopropanol is used as a solvent, so that the reaction temperature of the zinc powder and 1,2,3, 4-tetrachlorohexafluorobutane is higher than that of examples 1-4, and the method provided by the invention has the advantages that the reaction conditions of the zinc powder and 1,2,3, 4-tetrachlorohexafluorobutane are mild, and the energy consumption is low.
In addition, as can be seen from the comparison between example 1 and comparative example 1, the purity and yield of example 1 are obviously higher than those of comparative example 1 only due to the difference of the solvents, which shows that the method provided by the invention not only can reduce the reaction temperature and reduce the energy consumption, but also can improve the purity and yield of the hexafluorobutadiene.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (5)
1. A method for preparing hexafluorobutadiene by using a high-boiling point strong polar solvent is characterized in that: the method comprises the following steps:
mixing zinc powder and a high-boiling point strong polar solvent, stirring, dropwise adding 1,2,3, 4-tetrachlorohexafluorobutane into the mixture for reaction when the temperature is 50-70 ℃, reacting for 1-2 h after dropwise adding 1,2,3, 4-tetrachlorohexafluorobutane to obtain a reaction product, drying the product, collecting the product in a cold trap, and collecting the collected gas, namely, the hexafluorobutadiene;
the high boiling point strong polar solvent is a solvent with a boiling point of more than 180 ℃ and a polarity of more than 5.0;
the mass ratio of the zinc powder to the 1,2,3, 4-tetrachlorohexafluorobutane is 2:1 to 5: 1;
the cold trap collection temperature is-50-6 ℃.
2. The method for preparing hexafluorobutadiene by using high boiling point strong polar solvent as claimed in claim 1, wherein: the high boiling point strong polar solvent is dimethyl sulfoxide, ethylene glycol or N-methyl pyrrolidone.
3. The method for preparing hexafluorobutadiene by using high boiling point strong polar solvent as claimed in claim 1, wherein: 1,2,3, 4-tetrachlorohexafluorobutane was added dropwise at a rate of 2 seconds.
4. The method for preparing hexafluorobutadiene by using high boiling point strong polar solvent as claimed in claim 1, wherein: the drying adopts zeolite, phosphorus pentoxide, calcium chloride or concentrated sulfuric acid with mass fraction of 98% as a drying agent.
5. The method for preparing hexafluorobutadiene by using high boiling point strong polar solvent as claimed in claim 1, wherein: the high-boiling point strong polar solvent is dimethyl sulfoxide, ethylene glycol or N-methyl pyrrolidone;
the dropping speed of the 1,2,3, 4-tetrachlorohexafluorobutane is 2 seconds;
the drying adopts zeolite, phosphorus pentoxide, calcium chloride or concentrated sulfuric acid with mass fraction of 98% as a drying agent.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2247104C2 (en) * | 2002-10-17 | 2005-02-27 | Общество с ограниченной ответственностью "НИЦ Экологическая и медицинская химия" (НИЦ Медхим) | Hexafluorobutadiene production process |
| CN101851145A (en) * | 2009-04-02 | 2010-10-06 | 浙江蓝天环保高科技股份有限公司 | Method for preparing 1,2,3,4-tetrachloro-hexafluoro butane |
| CN103922890A (en) * | 2014-04-17 | 2014-07-16 | 中蓝晨光化工研究设计院有限公司 | Method of preparing fluorine-containing olefin |
| CN108083972A (en) * | 2017-12-28 | 2018-05-29 | 浙江博瑞电子科技有限公司 | A kind of method of reactive distillation synthesis hexachlorobutadiene |
| CN111675597A (en) * | 2020-06-17 | 2020-09-18 | 浙江省化工研究院有限公司 | Preparation method of hexafluoro-1,3-butadiene and intermediate thereof |
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- 2021-02-07 CN CN202110177453.1A patent/CN113004118A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2247104C2 (en) * | 2002-10-17 | 2005-02-27 | Общество с ограниченной ответственностью "НИЦ Экологическая и медицинская химия" (НИЦ Медхим) | Hexafluorobutadiene production process |
| CN101851145A (en) * | 2009-04-02 | 2010-10-06 | 浙江蓝天环保高科技股份有限公司 | Method for preparing 1,2,3,4-tetrachloro-hexafluoro butane |
| CN103922890A (en) * | 2014-04-17 | 2014-07-16 | 中蓝晨光化工研究设计院有限公司 | Method of preparing fluorine-containing olefin |
| CN108083972A (en) * | 2017-12-28 | 2018-05-29 | 浙江博瑞电子科技有限公司 | A kind of method of reactive distillation synthesis hexachlorobutadiene |
| CN111675597A (en) * | 2020-06-17 | 2020-09-18 | 浙江省化工研究院有限公司 | Preparation method of hexafluoro-1,3-butadiene and intermediate thereof |
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