Preparation method of cyclic perfluorosulfonyl imino salt
By using hexachloroacetone as a raw material, avoiding high temperature, high pressure and hazardous raw materials, and adopting mild reaction conditions to prepare 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonylimide salt, the problems of high risk and high cost in the existing technology are solved, and a safe and economical preparation method is achieved.
Patent Information
- Application Number
- CN202510723244.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-30
- Publication Date
- 2025-09-05
AI Technical Summary
The existing methods for preparing 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl imide salt have the problems of high risk and high production cost, especially the methods using hydrogen fluoride electrolysis and hexafluoropropylene oxide and I2 as raw materials to react under high temperature and pressure conditions.
Hexachloroacetone is used as raw material and is prepared through a series of steps including reaction, reduction, chlorination, fluorination and salification, avoiding the use of hydrogen fluoride electrolysis and high temperature and high pressure conditions, using relatively mild reaction conditions and low-cost raw materials.
It reduces production risks and costs, provides a safer and more economical synthesis route, and is suitable for industrial production.
Smart Images
Figure CN120590338A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the field of organic synthesis, and in particular to a method for preparing a cyclic perfluorosulfonyl imide salt. Background Art
[0002] 1,1,2,2,3,3-Hexafluoropropane-1,3-disulfonylimide is a cyclic perfluorosulfonylimide salt. As an important chemical intermediate, it is used to prepare organic molecules with specific structures and functions, such as fluorinated heterocyclic compounds and fluorinated amine compounds. It can also be used to synthesize fluorinated functional materials with special properties, such as fluorinated polymers, liquid crystal materials, and optoelectronic materials. This allows for the preparation of high-performance organic photovoltaic materials, light-emitting diode materials, and electromagnetic shielding materials. In addition, its lithium salt form can be used as an additive in lithium-ion battery electrolytes to enhance electrochemical properties such as cycle life, rate capability, and safety. Therefore, it is widely used in the fields of organic synthesis, lithium batteries, semiconductors, and photoresists.
[0003] The prior art discloses some methods for preparing 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonylimide salts, which generally use dibromopropane as a raw material and prepare the target product through a multi-step synthesis.
[0004] The above method uses anhydrous hydrogen fluoride to react by electrolysis, and the process is highly dangerous.
[0005] Another prior art discloses using hexafluoropropylene oxide and I2 as raw materials and using nickel as a catalyst to carry out a series of reactions to obtain the target product.
[0006] However, the hexafluoropropylene oxide and I2 used in this method are dangerous, and the reaction is carried out under high temperature and pressure conditions, resulting in high production costs.
[0007] Therefore, it is necessary to provide a new method for preparing 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonylimide salt, which can overcome the shortcomings of the above-mentioned existing methods. Summary of the Invention
[0008] In order to solve the above-mentioned technical problems, the present application provides a method for preparing a cyclic perfluorosulfonyl imide salt, wherein the structural formula of the cyclic perfluorosulfonyl imide salt is Among them, M + is K, Na or Li metal ion, and the preparation method comprises the following steps:
[0009] Step 1: reacting hexachloroacetone with a chlorinating agent to obtain octachloropropane;
[0010] Step 2: reacting octachloropropane with hydrogen fluoride pyridine to obtain 1,3-dichlorohexafluoropropane;
[0011] Step 3: reacting 1,3-dichlorohexafluoropropane with a reducing agent to obtain sodium 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonate;
[0012] Step 4: reacting sodium 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonate with a chlorinating agent to obtain 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonyl chloride;
[0013] Step 5: reacting 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonyl chloride with a fluorinating agent to obtain 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonyl fluoride;
[0014] Step 6: Reaction of 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonyl fluoride with an ammonium salt, followed by reaction with a base to obtain a cyclic perfluorosulfonyl imide salt; as follows:
[0015]
[0016] The above technical solution at least provides a method for preparing cyclic perfluorosulfonyl imide salts that is different from the prior art, and solves the problems of high risk and high production cost in the prior art. The present application does not use the method of hydrogen fluoride electrolysis. The anhydrous hydrogen fluoride used in the electrolysis process of hydrogen fluoride electrolysis and the by-product fluorine gas produced are highly toxic substances and are extremely corrosive to equipment and pipelines, thereby placing extremely high requirements on equipment and pipelines, increasing production costs, and being prone to explosion during the reaction process, which is highly dangerous. The preparation method adopted in the present application is safer than the hydrogen fluoride electrolysis method. In addition, another prior art uses hexafluoropropylene oxide and I2 as raw materials and reacts under high temperature and pressure conditions, while the present application uses hexachloroacetone as raw material and does not use I2. 2， The production cost is greatly reduced, and no pressurized reaction conditions are used, thereby further reducing the production risk. In summary, the preparation method disclosed in this application not only reduces the risk of the reaction but also reduces the production cost, providing a more advantageous synthesis route for cyclic perfluorosulfonyl imide salts.
[0017] Preferably, in the step 1, the molar ratio of the hexachloroacetone to the chlorinating agent is 1:(1-1.5);
[0018] Preferably, in the step 1, the reaction temperature is 180-220° C., and the reaction time is 6-8 hours.
[0019] Preferably, in the step 2, the molar ratio of octachloropropane to pyridine hydrogen fluoride is 1:(6-8);
[0020] Preferably, in the step 2, the reaction temperature is 25 to 50° C.; and the reaction time is 12 to 18 hours.
[0021] Preferably, in the step three, the molar ratio of the 1,3-dichlorohexafluoropropane to the reducing agent is 1:(2-2.7).
[0022] Preferably, in the step 3, the 1,3-dichlorohexafluoropropane and the reducing agent are reacted for 6 to 8 hours, and then the sodium salt is added to continue the reaction for 10 to 15 hours.
[0023] By adopting the above technical solution, the addition of sodium salt can enable the reaction to proceed in the forward direction more fully, thereby improving the yield of the step three reaction.
[0024] Preferably, in the step 3, the reaction temperature is 110-120°C;
[0025] Preferably, in step three, the sodium salt is sodium bicarbonate or sodium carbonate.
[0026] Preferably, in the step 4, the molar ratio of sodium 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonate to phosphorus pentachloride is 1:(2-2.7);
[0027] Preferably, in the step 4, the reaction temperature is 150-180°C;
[0028] Preferably, in step 4, the reaction time is 5 to 8 hours.
[0029] Preferably, in the step 5, the molar ratio of the 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonyl chloride to the fluorinating agent is 1:(2-2.7);
[0030] Preferably, in the step 5, the reaction temperature is 90-100°C;
[0031] Preferably, in step five, the reaction time is 5 to 8 hours.
[0032] Preferably, in step 1 or step 4, the chlorinating agent is one or more of phosphorus pentachloride, phosphorus trichloride and phosphorus oxychloride.
[0033] Preferably, in step three, the reducing agent is one or more of sodium sulfite, sodium bisulfite, sodium dithionite and sodium thiosulfate.
[0034] Preferably, in step five, the fluorinating agent is potassium fluoride or pyridine hydrogen fluoride.
[0035] By adopting the above technical solution, the reaction can proceed relatively smoothly and a better yield can be obtained under relatively mild reaction conditions, which has great advantages compared with the existing technology.
[0036] In summary, this application has the following beneficial effects:
[0037] 1. The preparation method provided in this application avoids the use of expensive reaction raw materials and high temperature and high pressure reaction conditions, greatly reducing production costs and improving production safety.
[0038] 2. The preparation method provided in this application adopts a synthetic route different from the prior art, providing a new idea for the preparation of cyclic perfluorosulfonyl imide salts. DETAILED DESCRIPTION
[0039] Example
[0040] The following example is a method for preparing a cyclic perfluorosulfonyl imide salt, namely 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl imide salt. The preparation method is as follows:
[0041]
[0042] Among them, M + It is K, Na or Li metal ion.
[0043] Example 1
[0044] Step 1: Add 68.5g of phosphorus pentachloride and 87.1g of hexachloroacetone to a polytetrafluoroethylene liner, heat to 180°C, react for 8 hours, cool to room temperature, add the reaction solution to ice water, and precipitate a solid. The solid is washed three times with 5% sodium bicarbonate, extracted three times with dichloromethane, and dried to obtain 84.1g of a solid with a yield of 80%. Repeat the preparation multiple times for later use.
[0045] Step 2: React 50.2 g of octachloropropane and 26.9 g of pyridine hydrofluoride (70% HF) at 25°C for 18 h. After the reaction, add saturated sodium bicarbonate to neutralize the reaction solution to a weak base. Extract the organic layer with dichloromethane and spin-dry to obtain 26.4 g of a solid with a yield of 76%. Repeat the preparation multiple times for later use.
[0046] Step 3: Add 4.0 g of 1,3-dichlorohexafluoropropane, 4.6 g of sodium sulfite, 1.5 g of sodium bicarbonate, 14 mL of water, and 7 mL of acetonitrile to a reaction flask. React at 110°C for 8 hours. Then, add 4.6 g of sodium sulfite and 1.5 g of sodium bicarbonate and continue the reaction for 10 hours. After the reaction, remove the solvent, extract the organic phase with ethyl acetate, spin dry, and add isopropyl ether for crystallization to yield 5.2 g of the product, with a yield of 81%. Repeat the preparation multiple times for later use.
[0047] Step 4: React 4.8 g of sodium 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonate and 5.6 g of phosphorus pentachloride at 150°C for 8 hours. After the reaction is complete and the mixture becomes molten, cool to room temperature and pour into ice water. Extract the oily substance at the bottom with dichloromethane three times, dry it, and spin dry it to obtain 3.9 g of the product, with a yield of 83%. Repeat the preparation multiple times for later use.
[0048] Step 5: Add 3.8 g of 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonic acid chloride to a reaction flask, dissolve in 60 mL of acetonitrile, add 1.4 g of potassium fluoride, and stir at 90°C for 8 h. After completion of the reaction, 2.5 g of product is obtained, with a yield of 73%. Repeat the preparation multiple times for later use.
[0049] Step 6: Dissolve 2.4 g of 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonyl fluoride in 1.2 g of acetonitrile, add 0.8 g of ammonium carbonate, and stir at 40°C for 4 h to obtain 1.8 g of the product, with a yield of 76%. Add 1.7 g of 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonylimine to 5 mL of tetrahydrofuran and 0.39 g of KOH, and heat under reflux at 65°C for 2 h. After the reaction, cool, filter, and spin-dry the filtrate to obtain 1.3 g of a solid product, with a yield of 75%.
[0050] Example 2
[0051] Step 1: Add 70.0g of phosphorus pentachloride and 59.0g of hexachloroacetone to the polytetrafluoroethylene liner, heat to 220°C for 6h, cool to room temperature after the reaction, add the reaction solution to ice water to precipitate the solid, take out the solid, wash it with 5% sodium bicarbonate three times, and then extract it with dichloromethane three times. After drying, 55.1g of solid was obtained, with a yield of 77%.
[0052] Step 2: 49.9 g of octachloropropane and 35.6 g of pyridine hydrofluoride (70% HF) were reacted at 50° C. for 12 h. After the reaction, saturated sodium bicarbonate was added to neutralize the reaction solution to a weak base. The organic layer was extracted with dichloromethane and dried to obtain 25.8 g of a solid with a yield of 75%.
[0053] Step 3: Add 11.9 g of 1,3-dichlorohexafluoropropane, 18.4 g of sodium sulfite, 5.4 g of sodium bicarbonate, 42 mL of water, and 21 mL of acetonitrile to a reaction flask. React at 120°C for 6 h. Then, add 18.4 g of sodium sulfite and 5.4 g of sodium bicarbonate and continue the reaction for 15 h. After the reaction, remove the solvent, extract the organic phase with ethyl acetate, spin dry, and add isopropyl ether for crystallization to yield 16.0 g of the product, with a yield of 83%.
[0054] Step 4: 15.0 g of sodium 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonate and 23.6 g of phosphorus pentachloride were reacted at 180° C. for 5 h. After the reaction was complete and the mixture was molten, it was cooled to room temperature and poured into ice water. There was oil at the bottom. Dichloromethane was added and extracted three times. After drying and spin-drying, 11.9 g of product was obtained with a yield of 81%.
[0055] Step 5: Add 11.5 g of 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonic acid chloride to the reaction flask, dissolve it in 180 mL of acetonitrile, add 5.2 g of potassium fluoride, and stir at 100°C for 8 hours. After the reaction, 7.8 g of product is obtained, with a yield of 75%.
[0056] Step six is the same as step six in Example 1 and will not be described again.
[0057] Example 3
[0058] Step 1: Add 70.0g of phosphorus pentachloride and 74.1g of hexachloroacetone to a polytetrafluoroethylene liner, heat to 200°C, and react for 7 hours. After the reaction is complete, cool to room temperature and add the reaction solution to ice water to precipitate a solid. Remove the solid, wash it three times with 5% sodium bicarbonate, extract it three times with dichloromethane, and dry it to obtain 73.4g of a solid with a yield of 82%. Repeat the preparation multiple times for later use.
[0059] Step 2: 50.2 g of octachloropropane and 31.4 g of pyridine hydrofluoride (70% HF) were reacted at 35° C. for 15 h. After the reaction, saturated sodium bicarbonate was added to neutralize the reaction solution to a weak base. Dichloromethane was added to extract the organic layer and the solution was dried to obtain 27.7 g of a solid with a yield of 80%.
[0060] Step 3: Add 11.9 g of 1,3-dichlorohexafluoropropane, 15.0 g of sodium sulfite, 4.5 g of sodium bicarbonate, 42 mL of water, and 21 mL of acetonitrile to a reaction flask. React at 115°C for 7 hours. Then, add 15.0 g of sodium sulfite and 4.5 g of sodium bicarbonate and continue the reaction for 12 hours. After the reaction, remove the solvent, extract the organic phase with ethyl acetate, spin dry, and add isopropyl ether for crystallization to yield 16.5 g of the product, with a yield of 86%.
[0061] Step 4: 14.4 g of sodium 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonate and 18.6 g of phosphorus pentachloride were reacted at 165 ° C for 6 h. After the reaction was completed, it became molten. After cooling to room temperature, it was poured into ice water. There was oil at the bottom. Dichloromethane was added and extracted three times. After drying and spin-drying, 11.6 g of product was obtained, with a yield of 82%.
[0062] Step 5: Add 11.6 g of 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonic acid chloride to the reaction flask, dissolve it in 180 mL of acetonitrile, add 4.2 g of potassium fluoride, stir at 95°C for 6 h, and the reaction is completed to obtain 8.4 g of product with a yield of 80%.
[0063] Step six is the same as step six in Example 1 and will not be described again.
[0064] Example 4
[0065] Step 1: Add 140.1g of phosphorus pentachloride and 111.4g of hexachloroacetone to a polytetrafluoroethylene liner, heat to 180°C, react for 8 hours, cool to room temperature, add the reaction solution to ice water, and precipitate a solid. Remove the solid, wash it three times with 5% sodium bicarbonate, extract it three times with dichloromethane, and dry it to obtain 94.2g of solid, with a yield of 70%. Repeat the preparation multiple times for later use.
[0066] Step 2: 100.1 g of octachloropropane and 80.5 g of pyridine hydrofluoride (70% HF) were reacted at 25° C. for 18 h. After the reaction, saturated sodium bicarbonate was added to neutralize the reaction solution to a weak base. The organic layer was extracted with dichloromethane and dried to obtain 49.8 g of a solid with a yield of 72%.
[0067] Step 3: Add 24.1g of 1,3-dichlorohexafluoropropane, 41.2g of sodium sulfite, 11.0g of sodium bicarbonate, 84mL of water, and 42mL of acetonitrile to a reaction flask. React at 110°C for 8 hours. Then, add 41.2g of sodium sulfite and 11.0g of sodium bicarbonate and continue the reaction for 10 hours. After the reaction, remove the solvent, extract the organic phase with ethyl acetate, spin dry, and add isopropyl ether for crystallization to obtain 29.5g of the product, with a yield of 76%.
[0068] Step 4: 29.5g of sodium 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonate and 51.8g of phosphorus pentachloride were reacted at 150°C for 8h. After the reaction was complete and the mixture was molten, it was cooled to room temperature and poured into ice water. There was oil at the bottom. Dichloromethane was added and extracted three times. After drying and spin-drying, 22.3g of product was obtained with a yield of 77%.
[0069] Step 5: Add 22.0 g of 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonic acid chloride to the reaction flask, dissolve it in 360 mL of acetonitrile, add 11.0 g of potassium fluoride, stir at 90°C for 8 hours, and the reaction is completed to obtain 15.3 g of product with a yield of 77%.
[0070] Step six is the same as step six in Example 1 and will not be described again.
[0071] Example 5
[0072] Step 1: Add 68.1g of phosphorus pentachloride and 87.1g of hexachloroacetone to a polytetrafluoroethylene liner and heat to 150°C for 10 hours. After the reaction is complete, cool to room temperature and add the reaction solution to ice water to precipitate a solid. Remove the solid and wash it three times with 5% sodium bicarbonate, then extract it three times with dichloromethane, and dry it to obtain 78.9g of a solid with a yield of 75%. Repeat the preparation multiple times for later use.
[0073] Step 2: 100.1 g of octachloropropane and 53.6 g of pyridine hydrofluoride (70% HF) were reacted at 20° C. for 20 h. After the reaction, saturated sodium bicarbonate was added to neutralize the reaction solution to a weak base. The organic layer was extracted with dichloromethane and dried to obtain 47.7 g of a solid with a yield of 69%.
[0074] Step 3: Add 24.1g of 1,3-dichlorohexafluoropropane, 27.5g of sodium sulfite, 9.2g of sodium bicarbonate, 84mL of water, and 42mL of acetonitrile to a reaction flask. React at 100°C for 10 hours. Then, add 27.5g of sodium sulfite and 9.2g of sodium bicarbonate and continue the reaction for another 8 hours. After the reaction, remove the solvent, extract the organic phase with ethyl acetate, spin dry, and add isopropyl ether for crystallization to yield 28.3g of the product, a yield of 73%. Repeat the preparation multiple times for later use.
[0075] Step 4: 29.9 g of sodium 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonate and 32.6 g of phosphorus pentachloride were reacted at 140°C for 10 h. After the reaction was complete and the mixture was molten, it was cooled to room temperature and poured into ice water. There was oil at the bottom. Dichloromethane was added and extracted three times. After drying and spin-drying, 20.1 g of product was obtained with a yield of 74%.
[0076] Step 5: Add 19.9 g of 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonic acid chloride to a reaction flask, dissolve it in 360 mL of acetonitrile, add 6.6 g of potassium fluoride, and stir at 80°C for 9 hours. After the reaction, 13.3 g of product is obtained, with a yield of 74%.
[0077] Step six is the same as step six in Example 1 and will not be described again.
[0078] Example 6
[0079] Step 1: Add 68.1g of phosphorus pentachloride and 87.1g of hexachloroacetone to the polytetrafluoroethylene liner, heat to 230°C for 5h, cool to room temperature after the reaction, add the reaction solution to ice water to precipitate the solid, take out the solid, wash it with 5% sodium bicarbonate three times, and then extract it with dichloromethane three times. After drying, 77.8g of solid was obtained, with a yield of 74%.
[0080] Step 2: 49.9 g of octachloropropane and 26.7 g of pyridine hydrofluoride (70% HF) were reacted at 55° C. for 10 h. After the reaction, saturated sodium bicarbonate was added to neutralize the reaction solution to a weak base. The organic layer was extracted with dichloromethane and dried to obtain 24.5 g of a solid with a yield of 71%.
[0081] Step 3: Add 24.1g of 1,3-dichlorohexafluoropropane, 27.5g of sodium sulfite, 9.2g of sodium bicarbonate, 84mL of water, and 42mL of acetonitrile to a reaction flask. React at 130°C for 5 hours. Then, add 27.5g of sodium sulfite and 9.2g of sodium bicarbonate and continue the reaction for 16 hours. After the reaction, remove the solvent, extract the organic phase with ethyl acetate, spin dry, and add isopropyl ether for crystallization to obtain 28.7g of the product, with a yield of 74%. Repeat the preparation multiple times for later use.
[0082] Step 4: React 29.6 g of sodium 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonate and 34.6 g of phosphorus pentachloride at 190°C for 4 hours. After the reaction is complete and the mixture becomes molten, cool to room temperature and pour into ice water. Extract the oily substance at the bottom with dichloromethane three times, dry it, and spin-dry it to obtain 22.0 g of the product, with a yield of 76%. Repeat the preparation multiple times for later use.
[0083] Step 5: Add 23.0 g of 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonic acid chloride to the reaction flask, dissolve it in 360 mL of acetonitrile, add 7.7 g of potassium fluoride, stir at 110°C for 4 hours, and the reaction is completed to obtain 15.8 g of product with a yield of 76%.
[0084] Step six is the same as step six in Example 1 and will not be described again.
[0085] Example 7
[0086] The difference between Example 7 and Example 1 is that:
[0087] Step 3: Add 24.1 g of 1,3-dichlorohexafluoropropane obtained in Example 1, 27.5 g of sodium sulfite, 84 mL of water, and 42 mL of acetonitrile to a reaction flask. React at 110°C for 8 h. Then, add an additional 27.5 g of sodium sulfite and continue the reaction for 10 h. After the reaction, remove the solvent, extract the organic phase with ethyl acetate, and extract by spin drying. Add isopropyl ether for crystallization to yield 26.4 g of the product, for a yield of 68%.
[0088] The other steps are the same.
[0089] Example 8
[0090] The difference between Example 8 and Example 1 is that:
[0091] Step 3: Add 24.1 g of 1,3-dichlorohexafluoropropane obtained in Example 1, 27.5 g of sodium sulfite, 9.2 g of sodium bicarbonate, 84 mL of water, and 42 mL of acetonitrile to a reaction flask and react at 110°C for 8 h. After the reaction, remove the solvent, add ethyl acetate to extract the organic phase, spin dry, and add isopropyl ether to crystallize to obtain 24.4 g of the product, with a yield of 63%.
[0092] The other steps are the same.
[0093] Example 9
[0094] The difference between Example 9 and Example 1 is that:
[0095] Step 3: Add 24.1 g of 1,3-dichlorohexafluoropropane obtained in Example 1, 27.5 g of sodium sulfite, 11.6 g of sodium carbonate, 84 mL of water, and 42 mL of acetonitrile to a reaction flask. The reaction was carried out at 110°C for 8 h. An additional 27.5 g of sodium sulfite and 11.6 g of sodium carbonate were added, and the reaction was continued for 10 h. After the reaction, the solvent was removed, and the organic phase was extracted with ethyl acetate. The organic phase was then dried and crystallized with isopropyl ether to obtain 30.7 g of the product, with a yield of 79%.
[0096] The other steps are the same.
[0097] Example 10
[0098] Step 1: Add 50.0g of phosphorus trichloride and 96.4g of hexachloroacetone to a polytetrafluoroethylene liner, heat to 180°C, react for 8 hours, cool to room temperature, add the reaction solution to ice water, and precipitate a solid. The solid is removed and washed three times with 5% sodium bicarbonate, then extracted three times with dichloromethane, and dried to obtain 88.4g of a solid with a yield of 76%. Repeat the preparation multiple times for later use.
[0099] Step 2: 49.9 g of octachloropropane and 27.6 g of pyridine hydrofluoride (70% HF) were reacted at 25° C. for 18 h. After the reaction, saturated sodium bicarbonate was added to neutralize the reaction solution to a weak base. The organic layer was extracted with dichloromethane and dried to obtain 26.5 g of a solid with a yield of 77%.
[0100] Step 3: Add 24.1 g of 1,3-dichlorohexafluoropropane, 22.7 g of sodium bisulfite, 9.2 g of sodium bicarbonate, 84 mL of water, and 42 mL of acetonitrile to a reaction flask. React at 110°C for 8 hours. Then, add 22.7 g of sodium bisulfite and 9.2 g of sodium bicarbonate and continue the reaction for 10 hours. After the reaction, remove the solvent, extract the organic phase with ethyl acetate, spin dry, and add isopropyl ether for crystallization to obtain 29.1 g of the product, with a yield of 75%.
[0101] Step 4: 27.1g of 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonic acid sodium salt and 20.9g of phosphorus trichloride were reacted at 150°C for 8h. After the reaction was completed and the mixture was molten, it was cooled to room temperature and poured into ice water. There was oil at the bottom. Dichloromethane was added and extracted three times. After drying and spin drying, 20.7g of product was obtained with a yield of 78%.
[0102] Step 5: Add 20.6 g of 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonic acid chloride to the reaction flask, dissolve it in 360 mL of acetonitrile, add 3.4 g of hydrogen fluoride pyridine, stir at 90°C for 8 hours, and the reaction is completed to obtain 12.1 g of product with a yield of 65%.
[0103] Step six is the same as step six in Example 1 and will not be described again.
[0104] Example 11
[0105] Step 1: Add 99.7g of phosphorus oxychloride and 172.1g of hexachloroacetone to the polytetrafluoroethylene liner, heat to 180°C for 8h, cool to room temperature after the reaction, add the reaction solution to ice water, precipitate the solid, take out the solid, wash it with 5% sodium bicarbonate three times, and then extract it with dichloromethane three times. After drying, 149.6g of solid was obtained, with a yield of 72%.
[0106] Step 2: 99.1 g of octachloropropane and 66.4 g of pyridine hydrofluoride (70% HF) were reacted at 25° C. for 18 h. After the reaction, saturated sodium bicarbonate was added to neutralize the reaction solution to a weak base. The organic layer was extracted with dichloromethane and dried to obtain 51.3 g of a solid with a yield of 75%.
[0107] Step 3: Add 24.1g of 1,3-dichlorohexafluoropropane, 38.0g of sodium dithionite, 18.3g of sodium bicarbonate, 84mL of water, and 42mL of acetonitrile to a reaction flask. React at 110°C for 8 hours. Then, add 38.0g of sodium dithionite and 18.3g of sodium bicarbonate and continue the reaction for 10 hours. After the reaction, remove the solvent, extract the organic phase with ethyl acetate, spin dry, and add isopropyl ether for crystallization to obtain 28.3g of the product, with a yield of 73%.
[0108] Step 4: 29.1g of 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonic acid sodium salt and 25.1g of phosphorus oxychloride were reacted at 150°C for 8h. After the reaction was completed and the mixture was molten, it was cooled to room temperature and poured into ice water. There was oil at the bottom. Dichloromethane was added and extracted three times. After drying and spin drying, 21.8g of product was obtained with a yield of 76%.
[0109] Steps 5 and 6 are the same as those in Example 1 and will not be described in detail.
[0110] Example 12
[0111] The difference between Example 12 and Example 1 is that:
[0112] Step 3: Add 24.1 g of 1,3-dichlorohexafluoropropane obtained in Example 1, 34.2 g of sodium thiosulfate, 18.3 g of sodium bicarbonate, 84 mL of water, and 42 mL of acetonitrile to a reaction flask. The reaction was carried out at 110°C for 8 h. An additional 34.2 g of sodium thiosulfate and 18.3 g of sodium bicarbonate were added, and the reaction was continued for 10 h. After the reaction, the solvent was removed, and the organic phase was extracted with ethyl acetate. The organic phase was then dried and crystallized with isopropyl ether to obtain 27.9 g of the product, with a yield of 72%.
[0113] The other steps are the same.
[0114] It is worth noting that in step 6 of the above embodiment, KOH, NaOH, LiOH, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, sodium methoxide, potassium methoxide, lithium methoxide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, etc. can also be used to provide K, Na or Li metal ions to obtain different cyclic perfluorosulfonyl imide salts.
[0115] It can be seen from the above examples that the present application does not carry out the reaction under high pressure conditions, and the raw materials used are inexpensive. Compared with the existing technology, the production cost is low and the reaction conditions are mild, which greatly reduces the risk of the reaction and is conducive to industrial production.
[0116] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.
Claims
1. A method for preparing a cyclic perfluorosulfonyl imide salt, wherein the structural formula of the cyclic perfluorosulfonyl imide salt is Among them, M + is a K, Na or Li metal ion, characterized in that The preparation method comprises the following steps: Step 1: reacting hexachloroacetone with a chlorinating agent to obtain octachloropropane; Step 2: reacting octachloropropane with hydrogen fluoride pyridine to obtain 1,3-dichlorohexafluoropropane; Step 3: reacting 1,3-dichlorohexafluoropropane with a reducing agent to obtain sodium 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonate; Step 4: reacting sodium 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonate with a chlorinating agent to obtain 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonyl chloride; Step 5: reacting 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonyl chloride with a fluorinating agent to obtain 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonyl fluoride; Step 6: Reaction of 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonyl fluoride with an ammonium salt, followed by reaction with a base to obtain a cyclic perfluorosulfonyl imide salt; as follows:
2. The preparation method according to claim 1, characterized in that In the step 1, the molar ratio of the hexachloroacetone to the chlorinating agent is 1:(1-1.5); Preferably, in the step 1, the reaction temperature is 180-220° C., and the reaction time is 6-8 hours.
3. The preparation method according to claim 1, characterized in that In the step 2, the molar ratio of octachloropropane to pyridine hydrogen fluoride is 1:(6-8); Preferably, in the step 2, the reaction temperature is 25 to 50° C.; and the reaction time is 12 to 18 hours.
4. The preparation method according to claim 1, characterized in that In the step three, the molar ratio of the 1,3-dichlorohexafluoropropane to the reducing agent is 1:(2-2.7).
5. The preparation method according to claim 4, characterized in that In the step 3, the 1,3-dichlorohexafluoropropane and the reducing agent are reacted for 6 to 8 hours, and then the sodium salt is added and the reaction is continued for 10 to 15 hours; Preferably, in the step 3, the reaction temperature is 110-120°C; Preferably, in step three, the sodium salt is sodium bicarbonate or sodium carbonate.
6. The preparation method according to claim 1, characterized in that In the step 4, the molar ratio of the sodium 1,1,2,2,3,3-hexafluoropropane-1,3-propanedisulfonate to phosphorus pentachloride is 1:(2-2.7); Preferably, in the step 4, the reaction temperature is 150-180°C; Preferably, in step 4, the reaction time is 5 to 8 hours.
7. The preparation method according to claim 1, characterized in that In the step 5, the molar ratio of the 1,1,2,2,3,3-hexafluoro-1,3-propanedisulfonyl chloride to the fluorinating agent is 1:(2-2.7); Preferably, in the step 5, the reaction temperature is 90-100°C; Preferably, in step five, the reaction time is 5 to 8 hours.
8. The preparation method according to any one of claims 1 to 7, characterized in that In step 1 or step 4, the chlorinating agent is one or more of phosphorus pentachloride, phosphorus trichloride and phosphorus oxychloride.
9. The preparation method according to any one of claims 1 to 7, characterized in that In the step three, the reducing agent is one or more of sodium sulfite, sodium bisulfite, sodium dithionite and sodium thiosulfate.
10. The preparation method according to any one of claims 1 to 7, characterized in that: In the step 5, the fluorinating agent is potassium fluoride or pyridine hydrogen fluoride.