CN110950735B - Method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by gas phase method - Google Patents
Method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by gas phase method Download PDFInfo
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Abstract
The invention discloses a method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by a gas phase method, which takes hexafluoro-2-chloro-2-butene as a raw material to obtain the 1,1,1,4,4, 4-hexafluoro-2-butyne by gas phase dehydrochlorination reaction under the catalysis of a dechlorination catalyst. The method has the advantages of simple process, economy, environmental protection and easy industrialization.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by a gas phase method.
Background
1,1,1,4,4, 4-hexafluoro-2-butyne is an important fluorine-containing fine chemical raw material, and can be used for synthesizing a key intermediate containing bis-trifluoromethyl stacking blocks and ODS substitutes and used as a monomer of a fluorine-containing polymer. The polymer has acid and alkali resistance, can be used for a window of high-pressure equipment, and is also a key intermediate for preparing cis (Z) hexafluoro-2-butene of a fourth-generation foaming agent.
In the reports of the prior art, the preparation methods of 1,1,1,4,4, 4-hexafluoro-2-butyne mainly comprise the following methods:
(1) preparation of 1,1,1,4,4, 4-hexafluoro-2-butyne by using perchlorobutadiene as raw material
Henne, A.L, Lizongzi, Henry N et al report a process route for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by fluorination of perchlorobutadiene as a starting material followed by dechlorination with zinc powder, distillation, and fractionation (Henne, A.L.J.Am.chem.Soc; Lizongzi. organic chemistry, 1987, 107-109; Henry N.Synthesis,1984,787-90). The reaction equation is as follows:
the zinc powder is used as dechlorination reaction in the route, the reaction heat release is large, the temperature is difficult to control, the selectivity is poor, the metal salt three wastes are large and difficult to treat, and the industrialization is difficult.
(2) 1,1,1,4,4, 4-hexafluoro-2-butyne is prepared by using 2-butynedioic acid as a raw material
Hasek et al report a method of preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by reacting 2-butynedioic acid as a raw material with sulfur tetrafluoride (W.R.Hasek.J.am.chem.Soc.1960, 543-551). The reaction equation is as follows:
the main problems of the technical route are that the adopted raw materials are not easy to obtain, the sulfur tetrafluoride is expensive, and the method is not suitable for industrial production.
(3) Preparation of 1,1,1,4,4, 4-hexafluoro-2-butyne by using hexafluoropropylene as raw material
CN104945220B reports a method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne using hexafluoropropylene as a raw material. The reaction equation is as follows:
(1)CHCl 3 +CF 3 CF＝CF 2 →CCl 3 CF 2 CHFCF 3
(2)CCl 3 CF 2 CHFCF 3 +HF→CF 3 CF 2 CHFCF 3 +HCl
(3)CF 3 CF 2 CHFCF 3 →CF 3 CF＝CFCF 3 +CF 3 C≡CCF 3
the technical route has long steps, the raw material price is high, olefin byproducts are generated, and the selectivity and the purity of the 1,1,1,4,4, 4-hexafluoro-2-butyne are not high.
(4) Preparation of 1,1,1,4,4, 4-hexafluoro-2-butyne by using hexafluoro-2-chloro-2-butene as raw material
CN104684877A reports a process route for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by liquid phase saponification using hexafluoro-2-chloro-2-butene as raw material, and the reaction equation is as follows:
the technical route solves the problems of high price of raw materials and low selectivity and purity of 1,1,1,4,4, 4-hexafluoro-2-butyne, but adopts a liquid phase saponification method, needs a certain amount of surfactant, generates a large amount of metal salt wastewater, is difficult to treat and faces the challenge of environmental protection.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by a gas phase method, which has the advantages of simple process, economy, environmental protection and easy industrialization.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a process for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by gas-phase method features that the hexafluoro-2-chloro-2-butene is used as raw material, and the 1,1,1,4,4, 4-hexafluoro-2-butyne is obtained through gas-phase dehydrochlorination reaction under the catalysis of dechlorination catalyst.
The dechlorination catalyst is preferably a supported or unsupported metal halide.
The metal halide is preferably halide of Cr, Ba, Cs, Ni, Fe, Zn and Co.
The metal halide is more preferably one or more of barium chloride, ferric chloride, cesium fluoride, zinc chloride, chromium chloride, cobalt bromide and barium iodide.
The contact time of the gas-phase dehydrochlorination reaction is preferably 0.5-60 s, and the reaction temperature is preferably 50-800 ℃.
The contact time of the gas-phase dehydrochlorination reaction is more preferably 1-30 s, and the reaction temperature is more preferably 100-300 ℃.
The invention takes hexafluoro-2-chloro-2-butene as raw material to prepare 1,1,1,4,4, 4-hexafluoro-2-butyne by gas-phase dehydrochlorination under the catalysis of a dechlorination catalyst. The method has the advantages of simple process, high selectivity, economy, environmental protection and continuous production, solves the problems of high raw material price, complex route, more three wastes, low selectivity and the like, avoids the consumption of dechlorinating agent, the addition of surface activity and the generation of a large amount of three wastes by adopting a liquid phase method, is more environment-friendly and economical, and has industrial prospect.
The reaction equation of the invention is as follows:
the reactor of the invention can adopt a corrosion-resistant reactor which is conventional in the field, such as a corrosion-resistant fixed bed reactor which can be selected from Hastelloy, lnconel, Monel, Nickel and silicon carbide materials.
The invention provides a method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne in a gas phase, which is characterized in that hexafluoro-2-chloro-2-butene passes through a fixed bed reactor and is subjected to dehydrochlorination reaction under the action of a dechlorination catalyst to prepare the 1,1,1,4,4, 4-hexafluoro-2-butyne. The initial product containing 1,1,1,4,4, 4-hexafluoro-2-butyne obtained by the invention can obtain the product with the required purity by the conventional rectification operation in the field.
The reaction temperature has great influence on the reaction, and a polymerization by-product is generated when the reaction temperature is too high, so that the selectivity of the product is reduced; the reaction temperature is too low, the reaction rate is low or even no reaction is carried out. Therefore, the reaction temperature is 50-800 ℃, preferably 100-300 ℃.
The contact time of the dehydrochlorination reaction has great influence on the reaction, the contact time of the dehydrochlorination reaction is too long, the number of byproducts is large, and the selectivity of the product is reduced; the contact time is too short and the conversion of the feedstock is too low. Therefore, the reaction contact time is 0.5 to 60s, preferably 1 to 30 s.
Compared with the prior art, the invention has the following advantages:
1. compared with other routes, the method for dehydrochlorination by gas phase catalysis shortens the reaction steps, simplifies the operation, can realize continuous reaction, obviously simplifies the process and has industrial prospect;
2. the method is environment-friendly, and the consumption of a dechlorinating agent and the addition of surface activity are avoided by adopting a catalytic dehydrochlorination mode, so that the generation of a large amount of three wastes by adopting a liquid phase method is avoided, and the method is more environment-friendly and economic;
3. the cost is low, the raw materials are cheap and easy to obtain, the three-waste treatment cost is low, and the production cost is obviously reduced;
4. the reaction efficiency is high, the conversion rate of the raw material hexafluoro-2-chloro-2-butene is more than 95%, and the selectivity of the product 1,1,1,4,4, 4-hexafluoro-2-butyne is more than 98%.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples.
Example 1:
introducing hexafluoro-2-chloro-2-butene into a Hardgrove alloy tube fixed bed reactor with the inner diameter of 30mm and containing 30ml of barium chloride catalyst at the flow rate of 15.9g/min, controlling the contact time to be 1s and the reaction temperature to be 100 ℃, collecting a crude product and then carrying out chromatographic analysis, wherein the conversion rate of the hexafluoro-2-chloro-2-butene is 97 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-butyne is 99 percent.
Example 2:
and introducing hexafluoro-2-chloro-2-butene into a silicon carbide tube fixed bed reactor with 30ml of ferric chloride catalyst and an inner diameter of 30mm at the flow rate of 0.53g/min, controlling the contact time for 30s and the reaction temperature to 300 ℃, collecting a crude product, and performing chromatographic analysis, wherein the conversion rate is 96 percent, and the selectivity of 1,1,1,4,4, 4-hexafluoro-2-butyne is 98 percent.
Example 3:
introducing hexafluoro-2-chloro-2-butene into a fixed bed reactor which is filled with 30ml of cesium fluoride catalyst and has an inner diameter of 30mm lnconel tube at the flow rate of 3.18g/min, controlling the contact time to be 5s and the reaction temperature to be 150 ℃, collecting a crude product and then carrying out chromatographic analysis, wherein the conversion rate of the hexafluoro-2-chloro-2-butene is 95.5 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-butyne is 99 percent.
Example 4:
introducing hexafluoro-2-chloro-2-butene into a Nickel tube fixed bed reactor with the inner diameter of 30mm and containing 30ml of barium fluoride catalyst at the flow rate of 1.59g/min, controlling the contact time for 10s and the reaction temperature to be 200 ℃, collecting crude products, and carrying out chromatographic analysis, wherein the conversion rate of the hexafluoro-2-chloro-2-butene is 98 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-butyne is 99 percent.
Example 5:
introducing hexafluoro-2-chloro-2-butene into a Monel tube fixed bed reactor with the inner diameter of 30mm and containing 30ml of zinc chloride catalyst at the flow rate of 1.06g/min, controlling the contact time for 15s and the reaction temperature at 250 ℃, collecting crude products, and carrying out chromatographic analysis, wherein the conversion rate of the hexafluoro-2-chloro-2-butene is 95 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-butyne is 98.5 percent.
Example 6:
introducing hexafluoro-2-chloro-2-butene into a silicon carbide tube fixed bed reactor with 30ml of chromium chloride catalyst and an inner diameter of 30mm at the flow rate of 0.80g/min, controlling the contact time for 20s and the reaction temperature at 280 ℃, collecting a crude product and then carrying out chromatographic analysis, wherein the conversion rate of the hexafluoro-2-chloro-2-butene is 95 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-butyne is 98 percent.
Example 7:
introducing hexafluoro-2-chloro-2-butene into a Nickel tube fixed bed reactor with the inner diameter of 30mm and filled with 30ml of barium chloride catalyst loaded on activated carbon at the flow rate of 0.64g/min, controlling the contact time to be 25s and the reaction temperature to be 250 ℃, collecting crude products and then carrying out chromatographic analysis, wherein the conversion rate of the hexafluoro-2-chloro-2-butene is 98 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-butyne is 99 percent.
Example 8:
introducing hexafluoro-2-chloro-2-butene into a silicon carbide tube fixed bed reactor with the inner diameter of 30mm and containing 30ml of cobalt bromide catalyst loaded on active carbon at the flow rate of 0.20g/min, controlling the contact time to be 8s and the reaction temperature to be 290 ℃, collecting crude products and carrying out chromatographic analysis, wherein the conversion rate of the hexafluoro-2-chloro-2-butene is 97 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-butyne is 99 percent.
Example 9:
introducing hexafluoro-2-chloro-2-butene into a silicon carbide tube fixed bed reactor with the inner diameter of 30mm and containing 30ml of barium iodide catalyst loaded on active carbon at the flow rate of 0.88g/min, controlling the contact time to be 18s and the reaction temperature to be 180 ℃, collecting crude products, and carrying out chromatographic analysis, wherein the conversion rate of the hexafluoro-2-chloro-2-butene is 98.5 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-butyne is 99 percent.
Claims (3)
1. A method for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne by a gas phase method is characterized in that hexafluoro-2-chloro-2-butene is taken as a raw material, and is subjected to gas phase dehydrochlorination reaction under the catalysis of a dechlorination catalyst to obtain the 1,1,1,4,4, 4-hexafluoro-2-butyne, wherein the dechlorination catalyst is one of barium chloride, cobalt bromide and barium iodide loaded on activated carbon.
2. The process for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne according to claim 1, wherein the contact time of the gas-phase dehydrochlorination reaction is 0.5 to 60 seconds, and the reaction temperature is 50 to 800 ℃.
3. The process for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne according to claim 1, wherein the contact time of the gas-phase dehydrochlorination reaction is 1 to 30s, and the reaction temperature is 100 to 300 ℃.
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| CN115772062A (en) * | 2021-09-06 | 2023-03-10 | 浙江省化工研究院有限公司 | Gas phase preparation method of 1, 4-hexafluoro-2-butyne |
| CN116143585B (en) * | 2023-04-04 | 2023-07-14 | 北京宇极科技发展有限公司 | Method for preparing hydrohaloolefine and method for preparing fluorine-containing alkyne |
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| US8530709B2 (en) * | 2010-05-21 | 2013-09-10 | Honeywell International Inc. | Process for the production of fluorinated alkenes |
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| CN106349007B (en) * | 2016-08-22 | 2019-06-11 | 巨化集团技术中心 | A kind of preparation method of Z-HFO-1336 |
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| CN110563547A (en) * | 2019-09-24 | 2019-12-13 | 浙江三美化工股份有限公司 | preparation method of 1,1,1,4,4, 4-hexafluoro-2-butene |
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