CN110981688B - Method for synthesizing 3,4, 4-trifluoro cyclobutene by gas phase catalysis - Google Patents

Method for synthesizing 3,4, 4-trifluoro cyclobutene by gas phase catalysis Download PDF

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CN110981688B
CN110981688B CN201911051327.0A CN201911051327A CN110981688B CN 110981688 B CN110981688 B CN 110981688B CN 201911051327 A CN201911051327 A CN 201911051327A CN 110981688 B CN110981688 B CN 110981688B
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柯巍
周彪
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China University of Mining and Technology Beijing CUMTB
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Abstract

The invention relates to a method for synthesizing 3,4, 4-trifluoro cyclobutene by gas phase catalysis, belonging to the field of organic chemical synthesis. The method for synthesizing the 3,4, 4-trifluoro cyclobutene is characterized in that: hexachlorobutadiene (molecular formula CCl)2＝CCl‑CCl＝CCl2) Chlorine gas (formula Cl)2) Anhydrous hydrogen fluoride (molecular formula HF) is reacted in gas phase to generate 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene (molecular formula Cyclo-CF) under the action of cyclic fluorination catalyst2-CFCl-CCl ═ CCl —). Then, 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene and hydrogen are reacted in the presence of hydrodechlorination catalyst to produce 3,4, 4-trifluoro cyclobutene (Cyclo-CF) in gaseous phase2-CFH-CH ═ CH —). The raw materials are cheap and convenient to obtain; the product is simple to separate and purify; the industrial production is easy to realize; less industrial three wastes.

Description

Method for synthesizing 3,4, 4-trifluoro cyclobutene by gas phase catalysis
Technical Field
The invention discloses a method for synthesizing 3,4, 4-trifluoro cyclobutene by gas phase catalysis, and relates to a method for synthesizing the 3,4, 4-trifluoro cyclobutene by an easily industrialized method.
Background
The 3,4, 4-trifluoro cyclobutene is a fluorine-containing olefin compound with wide application, is mainly applied to the fields of refrigerants, gas etching, fluorine-containing fine chemicals synthesis and the like, is unstable in the atmosphere and easy to degrade due to the carbon-carbon double bond and quaternary ring structure, has lower Global Warming Potential (GWP) and zero Ozone Depletion Potential (ODP), is an important ODP substitute and reaction intermediate, has higher economic value and industrial value, and has larger market demand.
There are few reports on the synthesis route of 3,4, 4-trifluorocyclobutene. The literature (Journal of Molecular Structure,1990,223, p.45-61) reports a method for synthesizing 3,4, 4-trifluorocyclobutene from perfluorocyclobutene and sodium tetrahydroborate in the presence of diethylene glycol dimethyl ether as a solvent at-15 ℃. The literature (European Journal of Organic Chemistry,2018,27-28, p.3867-3874) reports a process for synthesizing 82% of 3,4, 4-trifluorocyclobutene with lithium aluminum hydride under the action of tetrahydrofuran and dimethyl ether at-40 ℃, and the yield is reduced to 3% when the reaction temperature is reduced to-80 ℃. The method uses the industrially difficult-to-prepare perfluorocyclobutene and the expensive lithium salt as reaction raw materials, has high production cost and seriously restricts the popularization of the industrial production.
In summary, few reports about the industrial production of 3,4, 4-trifluorocyclobutene are reported at present, and the related technical problems are not broken through. The synthesis method in the prior literature has the defects of long technical route, harsh reaction conditions, extremely expensive raw materials and the like, and seriously limits the industrial production of the 3,4, 4-trifluorocyclobutene.
Disclosure of Invention
The invention aims to prepare the 3,4, 4-trifluoro cyclobutene with high yield by utilizing a simple reaction system and proper reaction conditions, and the raw materials are cheap and convenient to obtain; the product is simple to separate and purify; the synthesis process is safe and suitable for industrial production.
The invention relates to a method for synthesizing 3,4, 4-trifluoro cyclobutene by gas phase catalysis, belonging to the field of organic chemical synthesis. The method for synthesizing the 3,4, 4-trifluoro cyclobutene is characterized in that: hexachlorobutadiene (molecular formula CCl)2＝CCl-CCl＝CCl2) Chlorine gas (formula Cl)2) Anhydrous hydrogen fluoride (molecular formula HF) is reacted in gas phase to generate 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene (molecular formula Cyclo-CF) under the action of cyclic fluorination catalyst2-CFCl-CCl ═ CCl —). Then, 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene and hydrogen are reacted in the presence of hydrodechlorination catalyst to produce 3,4, 4-trifluoro cyclobutene (Cyclo-CF) in gaseous phase2-CFH-CH＝CH-)。
The first step of the invention is that cyclization and fluorination reaction are carried out simultaneously, hexachlorobutadiene, chlorine and anhydrous hydrogen fluoride are in gas phase to generate 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene under the action of a cyclic fluorination catalyst. Through experimental process data analysis, the reaction needs a fluorination catalyst with moderate acid strength and a cyclization catalyst with strong adsorption capacity. If the fluorination catalyst is too weak, too many chlorine atoms remain, and the activity of the catalyst is seriously affected. If the fluorination catalyst is too strong, the yield of 1,2, 3-trichloro-3, 4, 4-trifluorocyclobutene is severely affected. In the case of the cyclizing catalyst, if the adsorption ability is weak, the purpose of cyclization cannot be attained and the reaction product is still in a chain state. The multi-component composite catalyst designed by the invention has stronger adsorption capacity (cyclization capacity) and moderate acidity (fluorination capacity). Thus, the gas phase of the 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene can be stably generated. In order to adjust and obtain the catalyst with proper acidity, the catalyst is modified by different additives, wherein the additives are one or more composite components of Ni, Cu, Zn, Mg, Co and In. The second step of the invention is hydrodechlorination reaction, which adopts Pd/C catalyst. In order to adjust the proper catalytic performance, one or more of Ni, Fe, Al and Mn are adopted as an auxiliary agent.
Hexachlorobutadiene, chlorine and anhydrous hydrogen fluoride generate 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene In a gas phase under the action of a cyclic fluorination catalyst, wherein the cyclic fluorination catalyst is one or more composite component catalysts of Cr, Ni, Cu, Zn, Mg, Co and In.
Hexachlorobutadiene, chlorine and anhydrous hydrogen fluoride are subjected to gas phase reaction to generate the 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene under the action of a cyclic fluorination catalyst, and the gas phase reaction temperature is 100-550 ℃.
The method comprises the following steps of carrying out gas phase reaction on hexachlorobutadiene, chlorine and anhydrous hydrogen fluoride under the action of a cyclic fluorination catalyst to generate 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene, wherein the contact time of the gas phase reaction is as follows: 0.1-20 s.
Generating 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene from hexachlorobutadiene, chlorine and anhydrous hydrogen fluoride in a gas phase under the action of a cyclic fluorination catalyst, wherein the molar ratio of hexachlorobutadiene to chlorine to anhydrous hydrogen fluoride is as follows: 1: 0.1 to 10: 5-20.
The 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene and hydrogen are subjected to gas phase generation to generate the 3,4, 4-trifluoro cyclobutene under the action of a hydrodechlorination catalyst, and the active component of the hydrodechlorination catalyst is one or more composite component catalysts of Pd, Ni, Fe, Al and Mn.
The 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene and hydrogen are subjected to gas phase generation to generate the 3,4, 4-trifluoro cyclobutene under the action of a hydrodechlorination catalyst, and a carrier of the hydrodechlorination catalyst is one of activated carbon, alumina, zeolite or a molecular sieve.
The 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene and hydrogen are reacted in the presence of hydrodechlorination catalyst to produce 3,4, 4-trifluoro cyclobutene, and the hydrodechlorination catalyst has active component content of 0.1-10.0%.
The 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene and hydrogen are subjected to gas phase reaction to generate the 3,4, 4-trifluoro cyclobutene under the action of a hydrodechlorination catalyst, and the gas phase reaction temperature is 80-250 ℃.
The 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene and hydrogen gas are reacted in a gas phase to generate the 3,4, 4-trifluoro cyclobutene under the action of a hydrodechlorination catalyst, wherein the contact time of the gas phase reaction is as follows: 0.5-40 s.
The invention has the following beneficial effects:
1. the hexachlorobutadiene used as the raw material is convenient to obtain and low in price.
2. The invention adopts a gas phase ring fluorination method, so that the industrial three wastes are less and the product yield is high. The production cost is greatly reduced because of less byproducts and three wastes.
3. The invention adopts a normal pressure gas phase fluorination method, thereby reducing the risk of industrial safety production. Is completely suitable for industrial production.
4. The process route of the invention belongs to a green process with safe production, wide raw material source, high product yield and less industrial three wastes.
Figure 1
Drawings
FIG. 1 is a diagram of an inventive process of the present invention.
Detailed Description
The present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art according to the basic idea of the invention, within the scope of the invention, as long as they do not depart from the basic idea of the invention.
Example 1
(1) The preparation method of the cyclic fluorination catalyst by adopting a coprecipitation method comprises the following steps:
CrCl with the molar ratio of 75:5:203，Co(NO3)2，In(NO3)3Mixing the solutions, dropwise adding 30 wt% of ammonia water into the mixed solution, adjusting the pH value to 9.0, precipitating, filtering, washing with deionized water, drying, and performing compression molding to obtain a precursor Cr-Co-In of the cyclic fluorination catalyst;
50ml of the precursor of the cyclic fluorination catalyst Cr-Co-In is put into a fixed bed reactor, and the fixed bed reactor is heated by an open-type tube heating furnace. The catalyst is dried for 10 hours under the protection of 100ml/min nitrogen and at the temperature of 1 ℃/min rising to 400 ℃, and then the temperature is reduced to 200 ℃. This completes the drying process of the cyclic fluorination catalyst.
Heating the reactor to 300 ℃, activating the catalyst by 100ml/min nitrogen and 20ml/min hydrogen fluoride for 10 hours; activating the catalyst for 10 hours by 100ml/min nitrogen and 50ml/min hydrogen fluoride; activating the catalyst for 10 hours by 50ml/min nitrogen and 100ml/min hydrogen fluoride; activating the catalyst by pure hydrogen fluoride for 10 hours at a rate of 100 ml/min; the temperature was raised to 400 ℃ and the catalyst was activated with 100ml/min of pure hydrogen fluoride for 10 hours. This completes the catalyst activation process. The specific surface area of the powder was 132.30m as determined by the BET method2The pyridine adsorption infrared spectrum (Py-FTIR) shows that the pyridine is a medium strong acid.
The reactor is heated to 190 ℃, hexachlorobutadiene of 1.0g/min, hydrogen fluoride of 48ml/min and chlorine of 43ml/min enter a mixing cavity together and are mixed evenly. Then, the reaction solution passes through the reactor to reach a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis. The GC results showed that the collected product contained 23% of 1,2, 3-trichloro-3, 4, 4-trifluorocyclobutene (Cyclo-CF)2-CClF-CCl ═ CCl-), 39% tetrafluorodichlorocyclobutene (formula Cyclo-CF)2-CF2-CCl ═ CCl-), 19% hexachlorobutadiene.
(2) The preparation process of the hydrodechlorination catalyst comprises the following steps:
4.8g of PdCl2And 3.3g MnCl2Dissolved in 200ml of deionized water and poured rapidly into a dried 200g solution having a specific surface area of 1000m2In the activated carbon per gram. And (4) slowly drying by adopting a rotary evaporator. Thus, the Pd-Mn/C catalyst was prepared.
10ml of Pd-Mn/C catalyst was charged into a fixed bed reactor, which was heated with an open tube furnace. The catalyst is dried for 10 hours under the protection of nitrogen gas of 300ml/min and the temperature is increased to 300 ℃ at the speed of 10 ℃/min, and then the temperature is reduced to 100 ℃. This completes the drying process of the catalyst.
Heating the reactor to 70 ℃, activating the catalyst by 100ml/min nitrogen and 20ml/min hydrogen for 10 hours; activating the catalyst for 10 hours by 100ml/min nitrogen and 50ml/min hydrogen; activating the catalyst for 10 hours by 50ml/min nitrogen and 100ml/min hydrogen; activating the catalyst by pure hydrogen at a rate of 100ml/min for 10 hours; the reactor was raised to a temperature of 200 ℃ and the catalyst was activated with 100ml/min pure hydrogen for 10 h. This completes the catalyst activation process. The specific surface area of the powder was 654.0m by the BET method2/g。
The reactor was heated to 210 ℃ and 0.1g/min 1,2, 3-trichloro-3, 4, 4-trifluorocyclobutene (66% purity) was mixed with 48ml/min hydrogen in a mixing chamber. Then, the reaction solution passes through the reactor to reach a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis. The GC results showed that the collected product contained 42% of 3,4, 4-trifluorocyclobutene (Cyclo-CF)2-CHF-CH ═ CH-), 18% of 3,4, 4-trifluorocyclobutalkane (Cyclo-CF)2-CHF-CH2-CH2-)。
Example 2
(1) The preparation method of the cyclic fluorination catalyst by adopting a coprecipitation method comprises the following steps:
CrCl with the molar ratio of 80:5:153，Mg(NO3)2，Cu(NO3)2The solutions were mixed, and 30 wt.% aqueous ammonia was added dropwise to the mixed solution to adjust the pH to 9.0. Precipitating and filtering, washing with deionized water, drying, and press-forming to obtain the cyclic fluorination catalystAnd the body is Cr-Mg-Cu.
50ml of the precursor of the cyclic fluorination catalyst Cr-Mg-Cu is introduced into a fixed bed reactor, and the fixed bed reactor is heated by an open-type tube heating furnace. The catalyst is dried for 10 hours under the protection of 100ml/min nitrogen and at the temperature of 1 ℃/min rising to 400 ℃, and then the temperature is reduced to 200 ℃. This completes the drying process of the cyclic fluorination catalyst.
Heating the reactor to 300 ℃, activating the catalyst by 100ml/min nitrogen and 20ml/min hydrogen fluoride for 10 hours; activating the catalyst for 10 hours by 100ml/min nitrogen and 50ml/min hydrogen fluoride; activating the catalyst for 10 hours by 50ml/min nitrogen and 100ml/min hydrogen fluoride; activating the catalyst by pure hydrogen fluoride for 10 hours at a rate of 100 ml/min; the temperature was raised to 400 ℃ and the catalyst was activated with 100ml/min of pure hydrogen fluoride for 10 hours. This completes the catalyst activation process. The specific surface area of the powder was 121.30m as determined by the BET method2Pyridine adsorption infrared spectroscopy (Py-FTIR) showed it to be a strong acid.
The reactor is heated to 230 ℃, hexachlorobutadiene of 1.0g/min, hydrogen fluoride of 53ml/min and chlorine of 17 ml/min enter a mixing cavity to be mixed evenly. Then, the reaction solution passes through the reactor to reach a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis. The GC results showed that the collected product contained 26% of 1,2, 3-trichloro-3, 4, 4-trifluorocyclobutene (Cyclo-CF)2-CClF-CCl ═ CCl —), 33% of tetrafluorodichlorocyclobutene (formula Cyclo-CF)2-CF2-CCl ═ CCl-), 1% hexachlorobutadiene.
(2) The preparation process of the hydrodechlorination catalyst comprises the following steps:
4.0g of PdCl2And 2.9g MnCl3Dissolved in 200ml of deionized water and poured rapidly into a dried 200g solution having a specific surface area of 1000m2In the activated carbon per gram. And (4) slowly drying by adopting a rotary evaporator. Thus, the Pd-Mn/C catalyst was prepared.
10ml of Pd-Mn/C catalyst was charged into a fixed bed reactor, which was heated with an open tube furnace. The catalyst is dried for 10 hours under the protection of nitrogen gas of 300ml/min and the temperature is increased to 300 ℃ at the speed of 10 ℃/min, and then the temperature is reduced to 100 ℃. This completes the drying process of the catalyst.
Heating the reactor to 70 ℃, activating the catalyst by 100ml/min nitrogen and 20ml/min hydrogen for 10 hours; activating the catalyst for 10 hours by 100ml/min nitrogen and 50ml/min hydrogen; activating the catalyst for 10 hours by 50ml/min nitrogen and 100ml/min hydrogen; activating the catalyst by pure hydrogen at a rate of 100ml/min for 10 hours; the reactor was raised to a temperature of 200 ℃ and the catalyst was activated with 100ml/min pure hydrogen for 10 hours. This completes the catalyst activation process. The specific surface area of the powder was 875.0m as determined by the BET method2/g。
The reactor was heated to 230 ℃ and 0.1g/min 1,2, 3-trichloro-3, 4, 4-trifluorocyclobutene (43% purity) was mixed with 34ml/min hydrogen in a mixing chamber. Then, the reaction solution passes through the reactor to reach a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis. The GC results showed that the collected product contained 27% of 3,4, 4-trifluorocyclobutene (Cyclo-CF)2-CHF-CH ═ CH-), 13% of 3,4, 4-trifluorocyclobutalkane (Cyclo-CF)2-CHF-CH2-CH2-)。

Claims (3)

1. A method for synthesizing 3,4, 4-trifluoro cyclobutene by gas phase catalysis is characterized in that: generating 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene from hexachlorobutadiene, chlorine and anhydrous hydrogen fluoride in gas phase under the action of a cyclic fluorination catalyst; then, the 1,2, 3-trichloro-3, 4, 4-trifluoro cyclobutene and hydrogen gas generate 3,4, 4-trifluoro cyclobutene in gas phase under the action of a hydrodechlorination catalyst; the hydrodechlorination catalyst is Pd-Mn/C, the content of active components of the hydrodechlorination catalyst is 0.1% -10.0%, the reaction temperature of a hydrodechlorination gas phase is 80-250 ℃, and the contact time is as follows: 0.5-40 s;
the cyclic fluorination catalyst is prepared by mixing the following components in a molar ratio of 75:5:20 Cr-Co-In or a molar ratio 80:5:15 Cr-Mg-Cu; the mole ratio of hexachlorobutadiene to chlorine to anhydrous hydrogen fluoride is as follows: 1: 0.1 to 10: 5-20.
2. The method as claimed in claim 1, wherein the hexachlorobutadiene, chlorine and anhydrous hydrogen fluoride are subjected to gas phase reaction to obtain 1,2, 3-trichloro-3, 4, 4-trifluorocyclobutene under the action of the cyclic fluorination catalyst, and the gas phase reaction temperature is 100-550 ℃.
3. The process of claim 1, wherein hexachlorobutadiene, chlorine and anhydrous hydrogen fluoride are subjected to gas phase reaction under the action of a cyclic fluorination catalyst to produce 1,2, 3-trichloro-3, 4, 4-trifluorocyclobutene, and the gas phase reaction is carried out for the following contact time: 0.1-20 s.
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