Method for continuously and cleanly producing perfluoroolefin epoxide by using hydrogen peroxide

By using hydrogen peroxide and catalyst systems in the micro reactor, the problems of low production efficiency and unstable quality of perfluoroolefin epoxides in the prior art are solved, and efficient and stable production results are achieved, and waste water and waste salt are avoided. produce.

CN119431276APending Publication Date: 2025-02-14FUJIAN ZHONGZHOU NEW MATERIAL TECH CO LTD

Patent Information

Application Number
CN202411573614.9
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2024-11-06
Publication Date
2025-02-14

AI Technical Summary

Technical Problem

In the production of perfluoroolefin epoxides, the prior art has problems of low production efficiency and unstable product quality, especially when using hypochlorite systems, a large amount of waste water and waste salt will be generated, and the reaction efficiency is low.

Method used

The hydrogen peroxide continuous cleaning production method is adopted, and the reaction is carried out under the action of a catalyst and a cocatalyst to synthesize perfluoro-2-methyl-2,3-epoxy pentane by using hydrogen peroxide as an oxidizing agent in the micro reactor. The selected catalyst is a Group V or Group VI metal composite with the general formula [MO4]2- or [XM12O40]n-, and the cocatalyst includes halogen ions, which improves oxidation and selectivity.

Benefits of technology

Achieve efficient and stable production of perfluoro-2-methyl-2,3-epoxide, avoiding wastewater and waste salt problems caused by hypochlorite system, and improving production efficiency and product quality stability sex.

✦ Generated by Eureka AI based on patent content.

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Abstract

The invention belongs to the field of fluorine-containing fine organic chemical synthesis, and particularly relates to a method for continuously and cleanly producing perfluoroolefin epoxide by using hydrogen peroxide. The invention relates to a method for continuously and cleanly producing perfluoroolefin epoxide by using hydrogen peroxide, which comprises the following steps of: reacting perfluoro-2-methyl-2-pentene serving as a raw material in the presence of a polar solvent and hydrogen peroxide serving as an oxidant under the action of a catalyst to obtain perfluoro-2-methyl-2, 3-epoxypentane. The method has the beneficial effects that the micro-reactor is used, and the oxidizing agent, the catalyst, the cocatalyst and the polar solvent are continuously introduced into the pipeline of the micro-reactor, so that the synthesis from the hexafluoropropylene dimer to the epoxy compound is completed in a short time.
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Description

Technical Field

[0001] The invention belongs to the field of synthesis of fluorine-containing fine organic chemicals, and in particular relates to a method for continuously and cleanly producing perfluoroolefin epoxides by using hydrogen peroxide. Background Art

[0002] Halon (bromofluoroalkanes) fire extinguishing agents have been gradually eliminated from the market due to their stable chemical structure and low boiling point. Under the action of ultraviolet rays, they can release free bromine atoms to destroy the ozone layer, causing environmental problems. Among the environmentally friendly and efficient fire extinguishing agents that replace halons and fluoroalkanes, a more prominent product is the Novec1230TM fireproof liquid developed by the American 3M Company, commonly known as perfluorohexanone, with a chemical formula of CF3CF2COCF(CF3)2. Perfluorohexanone is a liquid at room temperature and is easy to store and transport; it is easy to gasify, and heat can be transferred by taking a little technical measures, and fires can be extinguished and explosions can be suppressed in a similar way to gaseous fire extinguishing agents. Therefore, perfluorohexanone is a clean fire extinguishing agent with outstanding advantages of high fire extinguishing efficiency, safety, environmental protection and convenient daily maintenance.

[0003] Perfluoro-2-methyl-2,3-epoxypentane (CAS: 788-67-0) is an important intermediate in the general synthesis route of perfluorohexanone. It is an important fluorine-containing chemical that can be used as a fire extinguishing agent, cleaning agent, solvent and other purposes. At the same time, as an intermediate, in addition to being used to synthesize perfluorohexanone, it can also be used to synthesize a variety of fluorinated ether solvents, and has broad production applications and market prospects.

[0004] Perfluoro-2-methyl-2,3-epoxypentane is usually prepared by oxidation of perfluoro-2-methyl-2-pentene (CAS: 1584-03-8, hereinafter referred to as D2). The oxidation systems used are mainly the following:

[0005] 1. Hypochlorite system. Kolenko, IP and others used sodium hypochlorite to epoxidize D2 to obtain perfluoro-2-methyl-2,3-epoxypentane (Oxides of fluoroolefins. 1. New method for the synthesis of perfluorinated epoxyalkanes [J] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1979, (11), 2509-12). Patents CN107382692A and CN107879912A also use calcium hypochlorite or sodium hypochlorite as oxidants. However, in the process of scale-up production, it was found that the effective chlorine of the hypochlorite solution in the above method was only 8%-14%, and the dosage was large, which would produce a large amount of chloride wastewater; at the same time, the hypochlorite solution would corrode stainless steel, increasing the difficulty of reactor selection. In addition, since the hypochlorite solution is immiscible with the substrate, it is a heterogeneous chemical reaction, the reaction is slow, and there is an obvious scale-up effect.

[0006] 2. Nitrogen oxides of fatty amines. Ono, Taizo and Henderson, Philip used the nitrogen oxide of trimethylamine as an oxidant to epoxidize D2 to obtain perfluoro-2-methyl-2,3-epoxypentane (Novel epoxidation reaction of perfluoroalkenes with trimethylamine N-oxide and iodosylbenzene [J] Tetrahedron Letters, 2002, 43 (44), 7961-7965;). Similarly, there are also methods using the nitrogen oxide of triethylamine as an oxidant (Novel epoxidation reaction of perfluoroalkenes with triethylamine N-oxide [J] Asian Journal of Chemistry, 2012, 24 (5) 2357-2358;), the nitrogen oxide of tributylamine as an oxidant (Epoxidation reaction of perfluoroalkenes with tert-amine N-oxide [J] Chinese Chemical Letters, 23 (11), 1237-1239; 2012), etc. Sha, Min et al. used m-chloroperbenzoic acid as an oxidant to in situ oxidize tributylamine, etc., and then further epoxidized D2 (One-pot catalytic epoxidation reaction ofperfluoro-2-methyl-2-pentene with tri-nbutylamine N-oxide or N,N-Dimethylcyclohexylamine N-oxide[J]Advanced Materials Research(Durnten-Zurich,Switzerland),2013,685,357-361,6pp.), obtaining a higher yield.

[0007] 3. Oxygen system: Patent application CN106749108 uses molecular oxygen oxidation to synthesize perfluoro-2,3-epoxy-2-methylpentane.

[0008] 4. Hydrogen peroxide system. Patent application WO2012134803 uses a hydrogen peroxide potassium hydroxide system to epoxidize perfluoro-2-methyl-2-pentene to prepare perfluoro-2-methyl-2,3-epoxypentane.

[0009] Among the above schemes, the hydrogen peroxide system and the hypochlorite system are the methods with better prospects for industrial application. The selectivity of the hydrogen peroxide system oxidation is relatively low, and the hypochlorite system has higher conversion rate and selectivity, but it will produce more waste salt and high solid waste treatment costs. Summary of the invention

[0010] The technical problem to be solved by the present invention is to provide a method for continuously and cleanly producing perfluoroolefin epoxide by using hydrogen peroxide with high production efficiency and stable product quality.

[0011] In order to solve the above technical problems, the technical solution adopted by the present invention is: to provide a method for continuously and cleanly producing perfluoroolefin epoxide using hydrogen peroxide, comprising the following steps:

[0012] Taking perfluoro-2-methyl-2-pentene as a raw material, reacting with hydrogen peroxide (hydrogen peroxide) as an oxidant under polar solvent conditions and in the presence of a catalyst to obtain perfluoro-2-methyl-2,3-epoxypentane;

[0013] The selected catalyst has the general formula [MO4] 2- or [XM 12 O 40 ] n- , wherein M is selected from at least one of Group V or Group VI metals, and X is at least one of Si, P, and Ge.

[0014] Furthermore, in the above method for continuously cleaning and producing perfluoroolefin epoxide with hydrogen peroxide, a co-catalyst is added to the reaction, and the co-catalyst includes halogen ions. The inventors have found that in the presence of halogen ions, the oxidizing property of hydrogen peroxide can be enhanced and the selectivity can be improved by combining the main catalyst in this scheme.

[0015] Furthermore, in the above method for continuously cleaning and producing perfluoroolefin epoxide using hydrogen peroxide, the co-catalyst is one or more of sodium bromide, sodium chloride, ammonium bromide, and tetrabutylammonium bromide.

[0016] Furthermore, the above method for continuously cleaning and producing perfluoroolefin epoxides using hydrogen peroxide comprises at least one of the following technical features:

[0017] The polar solvent is one or more of acetonitrile, tetrahydrofuran, N,N-dimethylformamide, and N,N-dimethylacetamide;

[0018] The catalyst is one or more of phosphotungstic acid, phosphomolybdic acid, tungstic acid or sodium tungstate.

[0019] Furthermore, the above method for continuously cleaning and producing perfluoroolefin epoxides using hydrogen peroxide comprises at least one of the following technical features:

[0020] The mass ratio of perfluoro-2-methyl-2-pentene to the polar solvent is 1:1 to 20;

[0021] The molar ratio of perfluoro-2-methyl-2-pentene to the catalyst is 1:0.005-0.2;

[0022] The molar ratio of perfluoro-2-methyl-2-pentene to the oxidant is 1:0.5-3;

[0023] The molar ratio of perfluoro-2-methyl-2-pentene to the co-catalyst is 1:0.05-0.5;

[0024] The reaction temperature is 10°C to 70°C;

[0025] The reaction time is 2s to 5min.

[0026] Furthermore, the above method for continuously cleaning and producing perfluoroolefin epoxides using hydrogen peroxide comprises at least one of the following technical features:

[0027] The mass ratio of perfluoro-2-methyl-2-pentene to the polar solvent is 1:2-5;

[0028] The molar ratio of perfluoro-2-methyl-2-pentene to the catalyst is 1:0.01-0.1;

[0029] The molar ratio of perfluoro-2-methyl-2-pentene to the oxidant is 1:0.9-2;

[0030] The molar ratio of perfluoro-2-methyl-2-pentene to the co-catalyst is 1:0.1-0.3;

[0031] The reaction temperature is 35°C to 55°C;

[0032] The reaction time is 5s to 2min.

[0033] Furthermore, in the above method for continuously cleaning and producing perfluoroolefin epoxide using hydrogen peroxide, the mass percentage of hydrogen peroxide solute is 27.5% to 50%.

[0034] Furthermore, in the above method for continuously cleaning and producing perfluoroolefin epoxide with hydrogen peroxide, the reaction is a continuous flow reaction, the reaction adopts a microchannel reactor or a tubular reactor, and the tubular reactor is an oscillating flow tubular reactor or a dynamic tubular reactor.

[0035] The beneficial effects of the present invention are as follows: the present invention uses a microreactor, and continuously introduces an oxidant, a catalyst, a co-catalyst and a polar solvent into a pipeline of the microreactor to complete the synthesis from hexafluoropropylene dimer to epoxy compound in a short time. The specific advantages are as follows:

[0036] 1. A new process for preparing perfluoro-2-methyl-2,3-epoxypentane based on continuous catalytic oxidation of hexafluoropropylene dimer with hydrogen peroxide was developed;

[0037] 2. The process conditions are mild, the reaction yield is high, no hypochlorite is used, and the catalyst and co-catalyst can be recycled, which greatly avoids the generation of waste salt;

[0038] 3. The process is fully continuous, which greatly improves the production efficiency of perfluoro-2-methyl-2,3-epoxypentane and the quality stability of the product. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 The present invention is a schematic flow diagram of a method for continuously cleaning and producing perfluoroolefin epoxide using hydrogen peroxide according to a specific embodiment of the present invention. DETAILED DESCRIPTION

[0040] In order to explain the technical content, achieved objectives and effects of the present invention in detail, the following is an explanation in combination with the implementation modes and the accompanying drawings.

[0041] Example 1

[0042] See also Figure 1 , a method for continuously cleaning and producing perfluoroolefin epoxide using hydrogen peroxide, comprising the following steps:

[0043] The heat exchange temperature of the microchannel reactor is set to 35°C. Prepare material A: add 29g sodium tungstate and 98g ammonium bromide to 500g water, stir and set aside, prepare material B: 565g 30% (solute mass percentage) hydrogen peroxide, C: 0.9kg acetonitrile and material D: 1.5kg hexafluoropropylene dimer D2. Set the mass flow rate of material A to 6.3g / min, the mass flow rate of material B to 5.7g / min, the mass flow rate of material C to 9g / min, and the mass flow rate of material D to 15g / min. The three streams of materials A, B, and C are mixed through two T-type 1 / 8 tees at a time and then enter the microreactor with material D. The reaction temperature is 35°C, the residence time is 1.5min, and the outlet of the reaction liquid is connected to a continuous stratification tank. After continuous stratification, the lower organic phase is taken to determine the gas chromatography. The purity of perfluoro-2-methyl-2,3-epoxypentane is 58.6%, the conversion rate is 61%, and the yield is 57%.

[0044] Example 2

[0045] A method for continuously cleaning and producing perfluoroolefin epoxide using hydrogen peroxide comprises the following steps:

[0046] The heat exchange temperature of the microchannel reactor is set to 35°C. Prepare material A: add 25g of tungstic acid and 98g of ammonium bromide to 500g of water, stir and set aside, prepare material B: 565g of 30% hydrogen peroxide, C: 0.9kg of acetonitrile and material D: 1.5kg of hexafluoropropylene dimer D2. Set the mass flow rate of material A to 6.3g / min, the mass flow rate of material B to 5.7g / min, the mass flow rate of material C to 9g / min, and the mass flow rate of material D to 15g / min. The three streams of materials A, B, and C are mixed through two T-type 1 / 8 tees at a time and then enter the microreactor with material D. The reaction temperature is 35°C, the residence time is 1.5min, and the outlet of the reaction liquid is connected to a continuous stratification tank. After continuous stratification, the lower organic phase is taken to determine the gas chromatography. The purity of perfluoro-2-methyl-2,3-epoxypentane is 85.6%, the conversion rate is 84.3%, and the yield is 81%.

[0047] Example 3

[0048] A method for continuously cleaning and producing perfluoroolefin epoxide using hydrogen peroxide comprises the following steps:

[0049] The heat exchange temperature of the microchannel reactor is set to 35°C. Prepare material A: add 57g of phosphotungstic acid and 98g of ammonium bromide to 500g of water, stir and set aside, prepare material B: 565g30% hydrogen peroxide, C: 0.9kg of acetonitrile and material D: 1.5kg of hexafluoropropylene dimer D2. Set the mass flow rate of material A to 6.6g / min, the mass flow rate of material B to 5.7g / min, the mass flow rate of material C to 9g / min, and the mass flow rate of material D to 15g / min. The three streams of materials A, B, and C are mixed through two T-type 1 / 8 tees at a time and then enter the microreactor with material D. The reaction temperature is 35°C, the residence time is 1.5min, and the outlet of the reaction liquid is connected to a continuous stratification tank. After continuous stratification, the lower organic phase is taken to determine the gas chromatography. The purity of perfluoro-2-methyl-2,3-epoxypentane is 93.6%, the conversion rate is 92.6%, and the yield is 90%.

[0050] Example 4

[0051] A method for continuously cleaning and producing perfluoroolefin epoxide using hydrogen peroxide comprises the following steps:

[0052] The heat exchange temperature of the microchannel reactor is set to 35°C. Prepare material A: add 57g of phosphotungstic acid and 322g of tetrabutylammonium bromide to 500g of water, stir and set aside, prepare material B: 565g30% hydrogen peroxide, C: 0.9kg of acetonitrile and material D: 1.5kg of hexafluoropropylene dimer D2. Set the mass flow rate of material A to 8.7g / min, the mass flow rate of material B to 5.7g / min, the mass flow rate of material C to 9g / min, and the mass flow rate of material D to 15g / min. The three streams of materials A, B, and C are mixed through two T-type 1 / 8 tees at a time and then enter the microreactor with material D. The reaction temperature is 35°C, the residence time is 1.5min, and the outlet of the reaction liquid is connected to a continuous stratification tank. After continuous stratification, the lower organic phase is taken to determine the gas chromatography. The purity of perfluoro-2-methyl-2,3-epoxypentane is 95.6%, the conversion rate is 98.2%, and the yield is 94%.

[0053] Example 5

[0054] A method for continuously cleaning and producing perfluoroolefin epoxide using hydrogen peroxide comprises the following steps:

[0055] The heat exchange temperature of the microchannel reactor is set to 35°C. Prepare material A: add 57g of phosphotungstic acid and 322g of tetrabutylammonium bromide to 500g of water, stir and set aside, prepare material B: 565g30% hydrogen peroxide, C: 0.9kg of tetrahydrofuran and material D: 1.5kg of hexafluoropropylene dimer D2. Set the mass flow rate of material A to 8.7g / min, the mass flow rate of material B to 5.7g / min, the mass flow rate of material C to 9g / min, and the mass flow rate of material D to 15g / min. The three streams of materials A, B, and C are mixed through two T-type 1 / 8 tees at a time and then enter the microreactor with material D. The reaction temperature is 35°C, the residence time is 1.5min, and the outlet of the reaction liquid is connected to a continuous stratification tank. After continuous stratification, the lower organic phase is taken to determine the gas chromatography. The purity of perfluoro-2-methyl-2,3-epoxypentane is 95.5%, the conversion rate is 96.5%, and the yield is 92%.

[0056] Example 6

[0057] A method for continuously cleaning and producing perfluoroolefin epoxide using hydrogen peroxide comprises the following steps:

[0058] The heat exchange temperature of the microchannel reactor is set to 35°C. Prepare material A: add 57g of phosphotungstic acid and 322g of tetrabutylammonium bromide to 500g of water, stir and set aside, prepare material B: 340g50% hydrogen peroxide, C: 0.9kg of acetonitrile and material D: 1.5kg of hexafluoropropylene dimer D2. Set the mass flow rate of material A to 8.7g / min, the mass flow rate of material B to 3.4g / min, the mass flow rate of material C to 9g / min, and the mass flow rate of material D to 15g / min. The three streams of materials A, B, and C are mixed through two T-type 1 / 8 tees at a time and then enter the microreactor with material D. The reaction temperature is 35°C, the residence time is 1.5min, and the outlet of the reaction liquid is connected to a continuous stratification tank. After continuous stratification, the lower organic phase is taken for gas chromatography. The purity of perfluoro-2-methyl-2,3-epoxypentane is 95.3%, the conversion rate is 98%, and the yield is 95%.

[0059] Example 7

[0060] A method for continuously cleaning and producing perfluoroolefin epoxide using hydrogen peroxide comprises the following steps:

[0061] The heat exchange temperature of the microchannel reactor is set to 55°C. Prepare material A: add 57g of phosphotungstic acid and 322g of tetrabutylammonium bromide to 500g of water, stir and set aside, prepare material B: 565g30% hydrogen peroxide, C: 0.9kg of acetonitrile and material D: 1.5kg of hexafluoropropylene dimer D2. Set the mass flow rate of material A to 8.7g / min, the mass flow rate of material B to 5.7g / min, the mass flow rate of material C to 9g / min, and the mass flow rate of material D to 15g / min. The three streams of materials A, B, and C are mixed through two T-type 1 / 8 tees at a time and then enter the microreactor with material D. The reaction temperature is 55°C, the residence time is 1.5min, and the outlet of the reaction liquid is connected to a continuous stratification tank. After continuous stratification, the lower organic phase is taken to determine the gas chromatography. The purity of perfluoro-2-methyl-2,3-epoxypentane is 95.7%, the conversion rate is 98.2%, and the yield is 94%.

[0062] In order to illustrate the beneficial effects of the present invention, the following comparative examples are provided for comparison:

[0063] Comparative Example 1

[0064] A method for producing perfluoroolefin epoxide comprises the following steps:

[0065] 135 g of hexafluoropropylene dimer D2 and 135 g of anhydrous dichloromethane were added to the reactor and stirred evenly. 30% 270 g of hydrogen peroxide was added and reacted at 5°C for 10 hours. After the reaction was completed, it was cooled to 0°C and allowed to stand for 30 minutes. The lower layer was collected. The conversion rate of D2 was 1% and no perfluoro-2-methyl-2,3-epoxypentane was detected.

[0066] The above comparative examples show that the oxidizing property of hydrogen peroxide alone is not sufficient to oxidize hexafluoropropylene dimer, and a method for intensifying the reaction process needs to be studied.

[0067] Comparative Example 2

[0068] Compared with Example 4, tetrabutylammonium bromide was not added in this example.

[0069] A method for producing perfluoroolefin epoxide comprises the following steps:

[0070] The heat exchange temperature of the microchannel reactor is set to 35°C. Prepare material A: add 57g of phosphotungstic acid to 500g of water, stir and set aside, prepare material B: 565g30% hydrogen peroxide, C: 0.9kg acetonitrile and material D: 1.5kg hexafluoropropylene dimer D2. Set the mass flow rate of material A to 8.7g / min, the mass flow rate of material B to 5.7g / min, the mass flow rate of material C to 9g / min, and the mass flow rate of material D to 15g / min. The three streams of materials A, B, and C are mixed through two T-type 1 / 8 tees at a time and then enter the microreactor with material D. The reaction temperature is 35°C, the residence time is 1.5min, and the outlet of the reaction liquid is connected to a continuous stratification tank. After continuous stratification, the lower organic phase is taken to measure the gas chromatography, and the conversion rate is 2.5% and the yield is 1%.

[0071] The above comparative example shows that without adding a promoter, the conversion rate of the product in this example is significantly reduced, and the yield is also reduced accordingly.

[0072] By comparing Examples 4 and 7 with the following comparative examples, the reaction temperature conditions are compared and analyzed. When the reaction temperature is preferably between 35°C and 55°C, the production efficiency and product quality stability are optimal. The relevant experiments are as follows:

[0073] Comparative Example 3

[0074] A method for producing perfluoroolefin epoxide comprises the following steps:

[0075] The heat exchange temperature of the microchannel reactor is set to 10°C. Prepare material A: add 57g of phosphotungstic acid and 322g of tetrabutylammonium bromide to 500g of water, stir and set aside, prepare material B: 565g30% hydrogen peroxide, C: 0.9kg of acetonitrile and material D: 1.5kg of hexafluoropropylene dimer D2. Set the mass flow rate of material A to 8.7g / min, the mass flow rate of material B to 5.7g / min, the mass flow rate of material C to 9g / min, and the mass flow rate of material D to 15g / min. The three streams of materials A, B, and C are mixed through two T-type 1 / 8 tees at a time and then enter the microreactor with material D. The reaction temperature is 10°C, the residence time is 1.5min, and the outlet of the reaction liquid is connected to a continuous stratification tank. After continuous stratification, the lower organic phase is taken to determine the gas chromatography. The purity of perfluoro-2-methyl-2,3-epoxypentane is 23.6%, the conversion rate is 25.5%, and the yield is 21.5%.

[0076] Comparative Example 4

[0077] A method for producing perfluoroolefin epoxide comprises the following steps:

[0078] The heat exchange temperature of the microchannel reactor is set to 25°C. Prepare material A: add 57g of phosphotungstic acid and 322g of tetrabutylammonium bromide to 500g of water, stir and set aside, prepare material B: 565g30% hydrogen peroxide, C: 0.9kg of acetonitrile and material D: 1.5kg of hexafluoropropylene dimer D2. Set the mass flow rate of material A to 8.7g / min, the mass flow rate of material B to 5.7g / min, the mass flow rate of material C to 9g / min, and the mass flow rate of material D to 15g / min. The three streams of materials A, B, and C are mixed through two T-type 1 / 8 tees at a time and then enter the microreactor with material D. The reaction temperature is 25°C, the residence time is 1.5min, and the outlet of the reaction liquid is connected to a continuous stratification tank. After continuous stratification, the lower organic phase is taken to determine the gas chromatography. The purity of perfluoro-2-methyl-2,3-epoxypentane is 60.8%, the conversion rate is 62.5%, and the yield is 58.5%.

[0079] Comparative Example 5

[0080] A method for producing perfluoroolefin epoxide comprises the following steps:

[0081] The heat exchange temperature of the microchannel reactor is set to 70°C. Prepare material A: add 57g of phosphotungstic acid and 322g of tetrabutylammonium bromide to 500g of water, stir and set aside, prepare material B: 565g30% hydrogen peroxide, C: 0.9kg of acetonitrile and material D: 1.5kg of hexafluoropropylene dimer D2. Set the mass flow rate of material A to 8.7g / min, the mass flow rate of material B to 5.7g / min, the mass flow rate of material C to 9g / min, and the mass flow rate of material D to 15g / min. The three streams of materials A, B, and C are mixed through two T-type 1 / 8 tees at a time and then enter the microreactor with material D. The reaction temperature is 90°C, the residence time is 1.5min, and the outlet of the reaction liquid is connected to a continuous stratification tank. After continuous stratification, the lower organic phase is taken for gas chromatography. The purity of perfluoro-2-methyl-2,3-epoxypentane is 92.6%, the conversion rate is 99.5%, and the yield is 92.5%.

[0082] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention's specification and drawings, or directly or indirectly applied in related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for continuously cleaning and producing perfluoroolefin epoxide using hydrogen peroxide, characterized in that: The steps include: Taking perfluoro-2-methyl-2-pentene as a raw material, reacting with hydrogen peroxide as an oxidant in a polar solvent under the action of a catalyst to obtain perfluoro-2-methyl-2,3-epoxypentane; The selected catalyst has the general formula [MO4] 2- or [XM 12 O 40 ] n- , wherein M is selected from at least one of Group V or Group VI metals, and X is at least one of Si, P, and Ge.

2. The method for continuous clean production of perfluoroolefin epoxide using hydrogen peroxide according to claim 1, characterized in that: The reaction also includes a promoter, which includes a halide ion.

3. The method for continuous clean production of perfluoroolefin epoxide using hydrogen peroxide according to claim 2, characterized in that: The co-catalyst is one or more of sodium bromide, sodium chloride, ammonium bromide and tetrabutylammonium bromide.

4. The method for continuous clean production of perfluoroolefin epoxide using hydrogen peroxide according to claim 2, characterized in that: Include at least one of the following technical features: The polar solvent is one or more of acetonitrile, tetrahydrofuran, N,N-dimethylformamide, and N,N-dimethylacetamide; The catalyst is one or more of phosphotungstic acid, phosphomolybdic acid, tungstic acid or sodium tungstate.

5. The method for continuous clean production of perfluoroolefin epoxide using hydrogen peroxide according to claim 2, characterized in that: Include at least one of the following technical features: The mass ratio of perfluoro-2-methyl-2-pentene to the polar solvent is 1:1 to 20; The molar ratio of perfluoro-2-methyl-2-pentene to the catalyst is 1:0.005-0.2; The molar ratio of perfluoro-2-methyl-2-pentene to the oxidant is 1:0.5-3; The molar ratio of perfluoro-2-methyl-2-pentene to the co-catalyst is 1:0.05-0.5; The reaction temperature is 10°C to 70°C; The reaction time is 2s to 5min.

6. The method for continuous clean production of perfluoroolefin epoxide using hydrogen peroxide according to claim 2, characterized in that: Include at least one of the following technical features: The mass ratio of perfluoro-2-methyl-2-pentene to the polar solvent is 1:2-5; The molar ratio of perfluoro-2-methyl-2-pentene to the catalyst is 1:0.01-0.1; The molar ratio of perfluoro-2-methyl-2-pentene to the oxidant is 1:0.9-2; The molar ratio of perfluoro-2-methyl-2-pentene to the co-catalyst is 1:0.1-0.3; The reaction temperature is 35°C to 55°C; The reaction time is 5s to 2min.

7. The method for continuous clean production of perfluoroolefin epoxide using hydrogen peroxide according to claim 1, characterized in that: The solute mass percentage of the hydrogen peroxide is 27.5% to 50%.

8. The method for continuous clean production of perfluoroolefin epoxide using hydrogen peroxide according to claim 1, characterized in that: The reaction is a continuous flow reaction, and the reaction adopts a microchannel reactor or a tubular reactor, and the tubular reactor is an oscillating flow tubular reactor or a dynamic tubular reactor.

Citation Information

Patent Citations

  • Synthesis method and application of perfluoro(2-methyl-3-pentanone)

    CN107382692A

  • Continuous production process of perfluor-2-methyl-3-pentanone

    CN107879912A

  • Fluorinated oxiranes as organic rankine cycle working fluids and methods of using same

    WO2012134803A2

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  • Method for catalytically synthesizing perfluoroepoxide by using tungstate ionic liquid

    CN120554317A

  • Preparation method of perfluoro-2-methyl-2, 3-epoxypentane

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