CN110981689B - Method for synthesizing 3, 4-difluorocyclobutene by gas phase catalysis - Google Patents
Method for synthesizing 3, 4-difluorocyclobutene by gas phase catalysis Download PDFInfo
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Abstract
The invention relates to a method for synthesizing 3, 4-difluorocyclobutene by gas phase catalysis, belonging to the field of organic chemical synthesis. The method for synthesizing the 3, 4-difluorocyclobutene is characterized by comprising the following steps: hexachlorobutadiene (molecular formula CCl)2＝CCl‑CCl＝CCl2) Chlorine gas (formula Cl)2) Anhydrous hydrogen fluoride (formula HF) is reacted in the gas phase under the action of a cyclic fluorination catalyst to produce 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene (formula Cyclo-CFCl-CFCl-CCl ═ CCl-). Then, 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene and hydrogen are reacted in the presence of hydrodechlorination catalyst to produce 3, 4-difluorocyclobutene (Cyclo-CFH-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
Technical Field
The invention discloses a method for synthesizing 3, 4-difluorocyclobutene by gas-phase catalysis, and relates to a method for synthesizing 3, 4-difluorocyclobutene by an easily industrialized method.
Background
The 3, 4-difluorocyclobutene is a fluorine-containing olefin compound, does not contain chlorine atoms in molecules, has ozone layer depletion potential (ODP) of 0 and low Global Warming Potential (GWP), is mainly applied to the fields of grain fumigation, foaming agents, electronic etching, refrigerants and the like at present, and is very widely applied. 3, 4-difluorocyclobutene is reported to be a very important tire rubber additive. With the gradual increase of the automobile market, the industrial demand of the 3, 4-difluorocyclobutene is sharply increased, and the market demand is vigorous.
There are few reports on the synthesis route of 3, 4-difluorocyclobutene. The literature (Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy,1994,50(2), p.191-202) reports a process for producing 3, 4-difluorocyclobutene with a content of 40% from dichlorocyclobutene by reaction with potassium fluoride and silver fluoride at 100 ℃ under a reduced pressure of 0.001Torr for 2 hours. The method uses the dichloro cyclobutene which is not easy to be prepared industrially as a raw material, greatly improves the cost and seriously restricts the popularization of the industrial production.
In summary, few reports about the synthesis route of 3, 4-difluorocyclobutene are reported at present, and the related technical problems are not broken through. The reported route for preparing 3, 4-difluorocyclobutene by adopting dichlorocyclobutene has the defects of long route, harsh conditions and expensive raw materials, and limits the industrial production of the 3, 4-difluorocyclobutene.
Disclosure of Invention
The invention aims to prepare the 3, 4-difluorocyclobutene with high yield by utilizing a simple reaction system and proper reaction conditions, and the invention has cheap raw materials and convenient sources; the product is simple to separate and purify; the synthesis process is safe and suitable for industrial production.
The invention relates to a gas-phase catalytic synthesis of 3, 4-difluorocyclobutene, belonging to the field of organic chemical synthesis. The method for synthesizing the 3, 4-difluorocyclobutene is characterized by comprising the following steps: hexachlorobutadiene (molecular formula CCl)2＝CCl-CCl＝CCl2) Chlorine gas (formula Cl)2) Anhydrous hydrogen fluoride (formula HF) is reacted in the gas phase under the action of a cyclic fluorination catalyst to produce 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene (formula Cyclo-CFCl-CFCl-CCl ═ CCl-). Then, 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene and hydrogen are reacted in the presence of hydrodechlorination catalyst to produce 3, 4-difluorocyclobutene (Cyclo-CFH-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, 4-tetrachloro-3, 4-difluorocyclobutene 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, 4-tetrachloro-3, 4-difluorocyclobutene 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, 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene can be stably produced in a gas phase. In order to adjust and obtain the catalyst with proper acidity, the invention adopts different auxiliary agents to modify the catalyst. The auxiliary agent is one or more 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, 4-tetrachloro-3, 4-difluorocyclobutene 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.
The hexachlorobutadiene, chlorine and anhydrous hydrogen fluoride generate 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene in a gas phase under the action of a cyclic fluorination catalyst, and the gas phase reaction temperature is 100-550 ℃.
Generating 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene from hexachlorobutadiene, chlorine and anhydrous hydrogen fluoride in a gas phase under the action of a cyclic fluorination catalyst, wherein the contact time of the gas phase reaction is as follows: 0.1-20 s.
Generating 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene 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, 4-tetrachloro-3, 4-difluorocyclobutene and hydrogen are subjected to gas phase generation to generate the 3, 4-difluorocyclobutene 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, 4-tetrachloro-3, 4-difluorocyclobutene and hydrogen are subjected to gas phase generation to generate the 3, 4-difluorocyclobutene 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, 4-tetrachloro-3, 4-difluorocyclobutene and hydrogen are subjected to gas phase generation to form the 3, 4-difluorocyclobutene under the action of a hydrodechlorination catalyst, and the content of active components of the hydrodechlorination catalyst is 0.1% -10.0%.
The 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene and hydrogen are subjected to gas phase reaction to generate the 3, 4-difluorocyclobutene under the action of a hydrodechlorination catalyst, wherein the gas phase reaction temperature is 80-250 ℃.
The method comprises the following steps of carrying out gas phase reaction on 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene and hydrogen under the action of a hydrodechlorination catalyst to generate the 3, 4-difluorocyclobutene, 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, has less industrial three wastes and high product yield, and greatly reduces the production cost because of less byproducts and three wastes.
3. The invention adopts the atmospheric pressure gas phase fluorination method, reduces the risk of industrial safety production and 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.
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 65:20:153，Co(NO3)2，Zn(NO3)2The solutions were mixed, and 30 wt% aqueous ammonia was added dropwise to the mixed solution to adjust the pH to 10.0. Precipitating and filtering, washing with deionized water, drying, and pressing to obtain a precursor Cr-Co-Zn of the cyclic fluorination catalyst;
50ml of the precursor of the cyclic fluorination catalyst Cr-Co-Zn 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 142.50m as determined by the BET method2Pyridine adsorption infrared spectroscopy (Py-FTIR) showed it to be a strong acid.
The reactor is heated to 200 ℃, hexachlorobutadiene of 1.0g/min, hydrogen fluoride of 75ml/min and chlorine of 32 ml/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, and the GC result showed that the collected product contained 15% of 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene (Cyclo-CFCl-CClF-CCl ═ CCl-) and 35% of tetrafluorodichlorocyclobutene (Cyclo-CF)2-CF2-CCl ═ CCl-), 18% hexachlorobutadiene.
(2) The preparation process of the hydrodechlorination catalyst comprises the following steps:
4.5g of PdCl2And 2.8g of NiCl3Dissolved in 200ml of deionized water and poured rapidly into a dried 200g solution having a specific surface area of 1000m2In the active carbon of/g, slow drying by a rotary evaporator is adopted, thus completing the preparation of the Pd-Ni/C catalyst.
10ml Pd-Ni/C catalyst was loaded 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 ℃, thereby completing 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 and catalyzing 100ml/min nitrogen and 50ml/min hydrogen for 10 hours; 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 temperature of the reactor was raised to 200 ℃ and the catalyst was activated with pure hydrogen gas at 100ml/min for 10 hours, thereby completing the catalyst activation process. The specific surface area of the powder was 712.0m as determined by the BET method2/g。
The reactor was heated to 200 ℃ and 0.1g/min 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene (80% purity) was mixed with 54ml/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, and the GC result showed that the collected product contained 55% of 3, 4-difluorocyclobutene (Cyclo-CFH-CHF-CH ═ CH-), and 24% of 3, 4-difluorocyclobutanealkane (Cyclo-CFH-CHF-CH-)2-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 80:10:103，Co(NO3)2，Fe(NO3)3The solutions were mixed, and 30 wt% aqueous ammonia was added dropwise to the mixed solution to adjust the pH to 8.0. Precipitating and filtering, washing with deionized water, drying, and pressing to obtain a precursor Cr-Co-Fe of the cyclic fluorination catalyst;
50ml of the precursor of the cyclic fluorination catalyst Cr-Co-Fe was put into a fixed bed reactor, and the fixed bed reactor was heated by an open 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; 100ml/min pure hydrogen fluoride activation catalystTaking the mixture for 10 hours; 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 99.30m 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 290 ℃, hexachlorobutadiene of 1.0g/min, hydrogen fluoride of 70ml/min and chlorine of 16 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 result showed that the collected product contained 22% of 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene (Cyclo-CF)2-CCl2-CCl ═ CCl-), 24% trifluorotrichlorocyclobutene (formula Cyclo-CF)2-CFCl-CCl ═ CCl —), 2% hexachlorobutadiene.
(2) The preparation process of the hydrodechlorination catalyst comprises the following steps:
9.0g of PdCl2And 2.1g FeCl3Dissolved in 200ml of deionized water and poured rapidly into a dried 200g solution having a specific surface area of 1000m2In the active carbon per gram, slow drying by a rotary evaporator is adopted. Thus, the Pd-Fe/C catalyst was prepared.
10ml Pd-Fe/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 861.0m as determined by the BET method2/g。
The reactor was heated to 260 ℃ at 0.1g/min 1,2,3,4-tetrachloro-3, 4-difluorocyclobutene (purity 89%) and 57ml/min hydrogen gas enter a mixing chamber to be mixed uniformly. 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 result showed that the collected product contained 31% of 3, 4-difluorocyclobutene (Cyclo-CFH-CH)F-CH ═ CH-), 18% of 3, 4-difluorocyclobutane (Cyclo-CFH-CHF-CH)2-CH2-)。
Claims (3)
1. A method for synthesizing 3, 4-difluorocyclobutene by gas phase catalysis is characterized in that: generating 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene from hexachlorobutadiene, chlorine and anhydrous hydrogen fluoride in a gas phase under the action of a cyclic fluorination catalyst; then, 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene and hydrogen gas generate 3, 4-difluorocyclobutene (with the molecular formula of Cyclo-CFH-CFH-CH ═ CH-) in a gas phase under the action of a hydrodechlorination catalyst;
the cyclic fluorination catalyst is prepared by mixing the following components in a molar ratio of 65:20:15 Cr-Co-Zn or a molar ratio 80:10:10 of Cr-Co-Fe composite component catalyst; wherein the temperature of the cyclic fluorination gas phase reaction is 100-550 ℃; the contact time is as follows: 0.1-20 s; the mole ratio of hexachlorobutadiene to chlorine to anhydrous hydrogen fluoride is as follows: 1: 0.1 to 10: 5 to 20; carrying out gas phase reaction on 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene and hydrogen under the action of a hydrodechlorination catalyst to generate the 3, 4-difluorocyclobutene, wherein the active component of the hydrodechlorination catalyst is Pd, and the auxiliary agent is Ni; the carrier of the hydrodechlorination catalyst is one of activated carbon, alumina, zeolite or molecular sieve;
the content of active components of the hydrodechlorination catalyst is 0.1-10.0%.
2. The process of claim 1, wherein 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene is reacted with hydrogen over a hydrodechlorination catalyst in the gas phase at a temperature of from 80 to 250 ℃ to form 3, 4-difluorocyclobutene.
3. The process of claim 1, wherein 1,2,3, 4-tetrachloro-3, 4-difluorocyclobutene is reacted with hydrogen over a hydrodechlorination catalyst in the vapor phase to form 3, 4-difluorocyclobutene, the vapor phase reaction having contact times: 0.5-40 s.
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