Preparation method of fluorosulfonate

Abstract

The invention provides a preparation method of fluorosulfonate, which comprises the following steps: 1) mixing bis (fluorosulfonyl) bisphenol phenyl ester, an organic solvent and alkali metal salt for hydrolysis reaction, and separating reaction liquid to obtain a water phase and an oil phase; 2) concentrating the oil phase obtained in the step 1) to obtain a bisphenol compound; and concentrating the water phase obtained in the step 1) to obtain a solid, and adding a poor solvent into the solid to purify and crystallize to obtain the fluorosulfonate. The method is simple to operate, the obtained bisphenol compound can be recycled, less three wastes are generated, the production cost is low, the yield and purity of a target product are high, and the requirements on production conditions are low, so that large-scale production and application are facilitated.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of battery, and relates to an electrolyte of a secondary battery, in particular to a preparation method of a fluorosulfonate. BACKGROUND

[0002] In the fields of power supply for people's livelihood such as mobile phones, notebook computers, and power supply for driving such as vehicle-mounted power supply for automobiles, fixed large power supply, and the like, non-aqueous electrolyte secondary batteries such as lithium secondary batteries are being put into practice. In recent years, the market has increasingly high performance requirements for non-aqueous electrolyte secondary batteries, and in particular, lithium secondary batteries need to be continuously improved towards high levels such as high capacity, high output, high-temperature storage characteristics, and cycle characteristics.

[0003] In particular, in the case of using lithium secondary batteries as power supply for electric vehicles, since electric vehicles require large energy when starting and accelerating, and high energy generated when decelerating must be effectively regenerated, lithium secondary batteries are required to have high output characteristics, input characteristics. At present, for the non-aqueous electrolyte of lithium secondary batteries, it is required to have initial capacity and high input-output characteristics, low internal resistance of the battery, and high capacity retention rate after durability tests such as high-temperature storage tests or cycle tests, and excellent input-output performance and impedance characteristics after durability tests.

[0004] Lithium fluorosulfonate as a high-quality non-aqueous electrolyte for lithium secondary batteries can better solve the above problems. In the prior art, the preparation methods of lithium fluorosulfonate mainly include the following:(1) a method of reacting fluorosulfonic acid or sulfur trioxide with lithium halide in anhydrous hydrofluoric acid to obtain fluorosulfonate;(2) a method of reacting fluorosulfonic acid and lithium carboxylate or lithium halide;(3) a method of mixing ammonium fluorosulfonate and lithium hydroxide aqueous solution to obtain trihydrate of fluorosulfonate;(4) a method of preparing lithium fluorosulfonate from alkyl fluorosulfonate and monophenyl fluorosulfonate. However, the substances such as sulfur trioxide and fluorosulfonic acid used in these reactions have high corrosiveness, and sulfuric acid and hydrofluoric acid gas with corrosiveness are generated, which not only causes corrosion of equipment and pollution of the environment, but also is difficult to operate in actual production process. For method (3), after synthesizing the ammonium salt, cation exchange of lithium salt is required, which is too cumbersome to operate, and ammonia is easily mixed in. For method (4), the yield of alkyl fluorosulfonate is low, and it is difficult to recover the low-boiling chlorohydrocarbon or alcohol generated after hydrolysis, resulting in increased production cost. In particular, phenol raw material is used for monophenyl fluorosulfonate, which is toxic and has a strong odor, polluting the environment, and is not suitable for industrial application.

[0005] Therefore, how to provide a preparation method of lithium fluorosulfonate, simplify the operation process, reduce the generation of by-products, improve the yield and purity of the target product, and reduce the production condition requirements, so as to facilitate large-scale production and application, has become an urgent problem to be solved by the technical personnel in the field. SUMMARY

[0006] In view of the above-mentioned disadvantages of the prior art, the purpose of the present application is to provide a preparation method of fluorosulfonate, which can produce fluorosulfonate with high purity under mild conditions in high yield by using difluorosulfonyl bisphenyl ester and alkali metal salt to react in an organic solvent, simplifies the operation process, reduces the generation of by-products, improves the yield and purity of the target product, and reduces the requirements of production conditions, thereby facilitating large-scale production application.

[0007] The technical scheme of the present application is as follows:

[0008] The present application provides a preparation method of fluorosulfonate, which comprises the following steps:

[0009] 1) mixing difluorosulfonyl bisphenyl ester, an organic solvent, and an alkali metal salt to perform a hydrolysis reaction, and separating the reaction solution to obtain an aqueous phase and an oil phase; wherein the structure of the difluorosulfonyl bisphenyl ester is shown in formula I,

[0010] In formula I, R is selected from alkyl, cycloalkyl, aralkyl, arycycloalkyl, -SO2- or -PO2-; R1 and R2 are independently H, halogen, alkyl, alkoxy or carboxyl;

[0011] 2) concentrating the oil phase obtained in step 1) to obtain a bisphenol compound; concentrating the aqueous phase obtained in step 1) to obtain a solid, adding a poor solvent to the solid to purify and crystallize, and obtaining fluorosulfonate.

[0012] By adopting the foregoing technical scheme, the present application has the following beneficial effects:

[0013] (1) The present application uses difluorosulfonyl bisphenyl ester and alkali metal salt (preferably a specific alkali metal salt) as raw materials, and can obtain fluorosulfonate by performing a simple hydrolysis reaction in an organic solvent (especially a polar aprotic solvent), thereby simplifying the operation process, reducing the generation of by-products, and improving the yield and purity of the target product, with the yield of the target product being up to 95% and the purity being up to 99.9%, while reducing the requirements of production conditions, thereby facilitating large-scale production application;

[0014] (2) Compared with the method of obtaining fluorosulfonate by reacting fluorosulfonic acid or sulfur trioxide with lithium halide in anhydrous hydrofluoric acid, the present application does not use raw materials such as fluorocarbon acid and sulfur trioxide, which are easy to produce corrosive substances, thereby reducing the danger and pollution of the production process, and reducing the requirements of the reaction equipment;

[0015] (3) Compared with the method of reacting fluorosulfonic acid with lithium carboxylate or lithium halide, the present invention avoids the product adsorption caused by the presence of carboxylic acid in the by-product, thereby further improving the purity of the product;

[0016] (4) Compared with the method of obtaining trihydrate of fluorosulfonate by mixing ammonium fluorosulfonate and lithium hydroxide aqueous solution, the present invention achieves the efficient acquisition of high-yield and high-purity fluorosulfonate by simple conventional operations under mild conditions without the need for tedious purification steps, which is conducive to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 Shown is the H NMR spectrum of the intermediate of bisphenol phenyl bisfluorosulfonate in Example 1 of the present invention;

[0018] Figure 2 Shown is the fluorine spectrum of the bis(fluorosulfonyl)bisphenol phenyl ester intermediate of Example 1 of the present invention. DETAILED DESCRIPTION

[0019] Hereinafter, embodiments of the method for preparing the fluorosulfonate provided by the present invention will be described in detail.

[0020] The "ranges" disclosed herein are defined in terms of lower and upper limits, where a given range is defined by selecting a lower limit and an upper limit, and the selected lower and upper limits define the boundaries of the particular range. Ranges defined in this manner can be inclusive or exclusive of the end values ​​and can be combined arbitrarily, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60 to 120 and 80 to 110 are listed for a particular parameter, it is understood that ranges of 60 to 110 and 80 to 120 are also contemplated. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, the following ranges are all contemplated: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5. In this application, unless otherwise indicated, the numerical range "a to b" is a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is simply an abbreviation for these numerical combinations. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0021] The present invention provides a method for preparing a fluorosulfonate, which comprises the following steps:

[0022] 1) mixing bis(fluorosulfonyl)bisphenol phenyl ester, an organic solvent, and an alkali metal salt to carry out a hydrolysis reaction, and separating the reaction solution to obtain an aqueous phase and an oil phase;

[0023] 2) concentrating the oil phase obtained in step 1) to obtain a bisphenol compound; concentrating the water phase obtained in step 1) to obtain a solid, adding a poor solvent to the solid to purify and crystallize, and obtaining a fluorosulfonate.

[0024] In the preparation method of the fluorosulfonate provided by the present application, step 1) is to mix the bisfluorosulfonyl biphenyl ester, the organic solvent and the alkali metal salt to perform a hydrolysis reaction, and the reaction solution is separated to obtain a water phase and an oil phase. The structure of the bisfluorosulfonyl biphenyl ester is shown in formula I,

[0025] In formula I, R is selected from an alkyl group, a cycloalkyl group, an aralkyl group, an arycycloalkyl group, -SO2- or -PO2-; alternatively, R is selected from a C1-C10 alkyl group, a C1-C10 cycloalkyl group, a C6-C20 aralkyl group, a C6-C20 arycycloalkyl group, -SO2- or -PO2-; further alternatively, R is selected from a C1-C6 alkyl group, a C1-C6 cycloalkyl group, a C6-C15 aralkyl group, a C6-C15 arycycloalkyl group, -SO2- or -PO2-; further alternatively, R is selected from a C1-C4 alkyl group, a C1-C4 cycloalkyl group, a C6-C12 aralkyl group, a C6-C12 arycycloalkyl group, -SO2- or -PO2-.

[0026] R1, R2 are independently H, halogen, an alkyl group, an alkoxy group or a carboxyl group. Alternatively, R1, R2 are independently H, halogen (for example, fluorine, chlorine, bromine, iodine), a C1-C10 alkyl group, a C1-C10 alkoxy group or a carboxyl group. Further alternatively, R1, R2 are independently H, fluorine, chlorine, bromine, iodine, a C1-C6 alkyl group, a C1-C6 alkoxy group or a carboxyl group. Further alternatively, R1, R2 are independently H, fluorine, chlorine, bromine, iodine, a C1-C4 alkyl group, a C1-C4 alkoxy group or a carboxyl group. Alternatively, R1, R2 can be the same group.

[0027] In step 1) of the present application, the preparation method of the bisfluorosulfonyl biphenyl ester comprises: taking a bisphenol compound and sulfonyl fluoride as starting materials to prepare a bisfluorosulfonyl biphenyl ester; wherein the structure of the bisphenol compound is shown in formula II:

[0028]

[0029] In formula II, R is selected from alkyl, cycloalkyl, aralkyl, aralkyl, -SO2- or -PO2-; alternatively, R is selected from C1-C10 alkyl, C1-C10 cycloalkyl, C6-C20 aralkyl, C6-C20 aralkyl, -SO2- or -PO2-; further alternatively, R is selected from C1-C6 alkyl, C1-C6 cycloalkyl, C6-C15 aralkyl, C6-C15 aralkyl, -SO2- or -PO2-; further alternatively, R is selected from C1-C4 alkyl, C1-C4 cycloalkyl, C6-C12 aralkyl, C6-C12 aralkyl, -SO2- or -PO2-.

[0030] R1, R2 are independently H, halogen, alkyl, alkoxy or carboxyl. Alternatively, R1, R2 are independently H, halogen (e.g. fluorine, chlorine, bromine, iodine), C1-C10 alkyl, C1-C10 alkoxy or carboxyl. Further alternatively, R1, R2 are independently H, fluorine, chlorine, bromine, iodine, C1-C6 alkyl, C1-C6 alkoxy or carboxyl. Further alternatively, R1, R2 are independently H, fluorine, chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 alkoxy or carboxyl. Alternatively, R1, R2 can be the same group.

[0031] The bis-fluorosulfonyl phenyl ester used in the reaction of the present application is selected from the preparation method of the bis-fluorosulfonyl phenyl ester of the present application. In the preparation method of the bis-fluorosulfonyl phenyl ester of the present application, the bisphenol compound is selected from one or more of bisphenol A, bisphenol B, bisphenol C, bisphenol AP, bisphenol E, bisphenol F, bisphenol M, bisphenol S, bisphenol Z.

[0032] In the preparation method of the bis-fluorosulfonyl phenyl ester of the present application, the sulfonyl fluoride is selected from one or more of sulfonyl fluoride, fluorosulfonyl chloride. Alternatively, sulfonyl fluoride is bubbled into the acetonitrile solution of the bisphenol compound, or fluorosulfonyl chloride is added dropwise.

[0033] In the preparation method of the bis-fluorosulfonyl phenyl ester of the present application, a solvent is further included, and the solvent is selected from one or more of dichloromethane, 1,2-dichloroethane, tetrachloroethane, carbon tetrachloride, acetonitrile.

[0034] In the preparation method of the bis-fluorosulfonyl phenyl ester of the present application, the molar ratio of the bisphenol compound to the sulfonyl fluoride reagent is 1:(2.0-2.3). Alternatively, the molar ratio of the bisphenol compound to the sulfonyl fluoride reagent can be, for example, 1:(2.0-2.1), 1:(2.1-2.3), 1:(2.0-2.2), 1:(2.2-2.3), etc.

[0035] The preparation method of the difluorosulfonyl bisphenyl ester provided by the present application further comprises an acid-binding agent selected from one or more of sodium carbonate, sodium bicarbonate, triethylamine, pyridine, and ethylenediamine; the molar ratio of the acid-binding agent to the bisphenol compound is (2.1-2.5):1; optionally, the molar ratio of the acid-binding agent to the bisphenol compound may be (2.1-2.3):1, (2.3-2.5):1, (2.1-2.2):1, (2.2-2.3):1, (2.3-2.4):1, (2.4-2.5):1, etc.

[0036] In the preparation method of the difluorosulfonyl bisphenyl ester provided by the present application, the reaction temperature is room temperature, and the reaction time is 6-8 hours. The reaction time may be selected to be 6-7 hours or 7-8 hours, etc.

[0037] In step 1) of the present application, the purity of the difluorosulfonyl bisphenyl ester is not particularly limited, but considering the convenience of product purification, the purity of the difluorosulfonyl bisphenyl ester is preferably above 99%.

[0038] In step 1) of the present application, the alkali metal salt is selected from one or more of an alkali metal carbonate, an alkali metal bicarbonate, an alkali metal oxide, an alkali metal hydroxide, or an alkali metal alcoholate. Optionally, the alkali metal carbonate is selected from one or more of lithium carbonate and lithium bicarbonate. The alkali metal oxide is lithium oxide. The alkali metal hydroxide is lithium hydroxide. The alkali metal alcoholate is selected from one or more of lithium methoxide, lithium ethoxide, lithium isopropoxide, and lithium tert-butoxide.

[0039] Among the above-mentioned alkali metal salts, from the perspective of reaction difficulty and easier access to high-purity products, the alkali metal carbonate, the alkali metal bicarbonate, the alkali metal oxide, the alkali metal hydroxide, or the alkali metal alcoholate is preferred.

[0040] The alkali metal salt used in the reaction of the present application can be directly used as a commercially available product, can be used after purification, or can be used after being prepared from other compounds, and the purity of the alkali metal salt is not particularly limited, and the purity of the alkali metal salt is preferably above 99%.

[0041] Further preferably, the alkali metal salt is selected from one or more of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium methoxide, lithium ethoxide, and lithium isopropoxide.

[0042] The molar ratio of the cation in the alkali metal salt to the bisfluorosulfonyl bisphenyl ester in the step 1) of the present application is not particularly limited, and the molar ratio of the cation in the alkali metal salt to the bisfluorosulfonyl bisphenyl ester is (2 to 6): 1. It can be (2 to 4): 1, (4 to 6): 1, (2 to 2.2): 1, (2.2 to 6): 1, (2 to 2.3): 1, (2.3 to 6): 1, (2 to 2.5): 1, (2.5 to 6): 1, (2 to 3): 1, (3 to 6): 1, (2 to 3.5): 1, (3.5 to 6): 1, (2 to 5): 1, (5 to 6): 1, or 2: 1, 2.2: 1, 2.3: 1, 2.5: 1, 3: 1, 3.5: 1, 4: 1, 5: 1, or 6: 1, but is not limited to the listed values. The cation in the alkali metal salt can be lithium ion. In the specific reaction procedure of the present application, the molar ratio of 2: 1 is preferred from the viewpoint of the cost of raw materials.

[0043] In the step 1) of the present application, when the amount of the bisfluorosulfonyl bisphenyl ester is increased relative to the cation in the alkali metal salt, a part of the acidic substance can remain in the resulting fluorosulfonate, and there is a risk that the quality and performance of the resulting fluorosulfonate are deteriorated. Therefore, the lower limit of the molar ratio of the cation in the alkali metal salt to the bisfluorosulfonyl bisphenyl ester is preferably 2 or more, and more preferably 2.05 or more, and the upper limit thereof is preferably 4 or less, more preferably 3 or less, and further preferably 2.4 or less. When the molar ratio of the cation in the alkali metal salt to the bisfluorosulfonyl bisphenyl ester is adjusted to the above range, a fluorosulfonate having high purity can be produced at a high yield without a complicated purification procedure.

[0044] In the step 1) of the present application, an organic solvent (non-aqueous organic solvent) is selected in the reaction procedure of the present application, and in order to effectively remove the residual solvent, an organic solvent having a boiling point of 200°C or lower is selected, and more preferably an organic solvent having an atmospheric boiling point of 150°C or lower, and further preferably an organic solvent having an atmospheric boiling point of 100°C or lower. As the organic solvent used in the reaction procedure of the present application, a polar organic solvent is particularly preferred, and further preferably a polar aprotic organic solvent, and for example, the organic solvent is selected from one or more of dichloromethane, 1,2-dichloroethane, tetrachloroethane, carbon tetrachloride, chloropropane, chlorobenzene, p-dichlorobenzene, and acetonitrile. Of the above organic solvents, dichloromethane and 1,2-dichloroethane are preferred, and the above organic solvents can be used alone or in combination, and in order not to complicate the operation, the use of a single solvent is preferred.

[0045] In the step 1) of the present application, the mass ratio of the organic solvent used in the present application to the bisfluorosulfonyl bisphenyl ester is not particularly limited, and is preferably 100 times or less, more preferably 50 times or less, and further preferably 25 times or less. In addition, the mass ratio of the organic solvent used in the reaction to the bisfluorosulfonyl bisphenyl ester is preferably 2 times or more, and more preferably 3 times or more. Within the above range, the production efficiency is excellent, and the fluorosulfonate is not excessively precipitated, resulting in unnecessary yield loss. Alternatively, the mass ratio of the organic solvent to the bisfluorosulfonyl bisphenyl ester is (3 to 10): 1. Further alternatively, it is (3 to 4): 1, (4 to 10): 1, (3 to 5): 1, (5 to 10): 1, (3 to 6): 1, (6 to 10): 1, (3 to 7): 1, (7 to 10): 1, (3 to 8): 1, (8 to 10): 1, (3 to 9): 1, (9 to 10): 1. For example, it can be 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, or 10: 1, but is not limited to the listed values, and other values not listed within the range are also applicable.

[0046] In the step 1) of the present application, water is used for hydrolysis, and the mass ratio of the water to the bisfluorosulfonyl bisphenyl ester is 1: (2 to 3), and is optionally 1: (2 to 2.5) or 1: (2.5 to 3).

[0047] In the step 1) of the present application, the reaction procedure temperature of the present application is not particularly limited, and is preferably 50°C or less, more preferably 40°C or less, and further preferably 30°C or less. In addition, the temperature at which the reaction is performed is preferably 20°C or more, more preferably 10°C or more, and further preferably 5°C or more. When the temperature at the start of the reaction procedure of the present application is within the above range, it is less likely to cause unpredictable side reactions, and the reaction rate is not excessively low. Alternatively, the reaction temperature is 20°C to 50°C, and is optionally 20°C to 25°C, 25°C to 50°C, 20°C to 30°C, 30°C to 50°C, 20°C to 35°C, 35°C to 50°C, 20°C to 40°C, 40°C to 50°C, 20°C to 45°C, or 45°C to 50°C. For example, it can be 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, or 50°C, but is not limited to the listed values, and other values not listed within the range are also applicable.

[0048] The order of the reaction process of the present application into the reaction system is not particularly limited, the solid base metal salt can be put into the stirring solution of bisfluorosulfonyl bisphenyl ester, or the bisfluorosulfonyl bisphenyl ester and solvent mixture can be added dropwise into the stirring mixture of base metal salt and organic solvent. Preferably, the specific way of mixing in step 1) is to mix the base metal salt and organic solvent first, and then add the fluorosulfonate dropwise after adjusting the temperature to 0-50°C. For example, the temperature can be adjusted to 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, but not limited to the listed values, other values not listed in this range are also applicable.

[0049] The feeding time in the reaction process of the present application is not particularly limited, preferably 12h or less, more preferably 12h or less, further preferably 10h or less. In addition, the feeding time in the reaction process of the present application is preferably 30min or more, more preferably 1h or more, further preferably 2h or more. By making the feeding time of the reaction process of the present application within the above range, a better reaction effect can be obtained with higher efficiency. Alternatively, the reaction time is 4h-12h. Alternatively, 4h-8h, 8h-12h, 4h-6h, 6h-8h, 8h-10h, 10h-12h. For example, it can be 4h, 6h, 8h, 10h or 12h, but not limited to the listed values, other values not listed in this range are also applicable.

[0050] The gas atmosphere in the reaction process of the present application is not particularly limited, and is preferably carried out under the protection of dry nitrogen and / or argon and other inert gases.

[0051] In step 1) of the present application, the reaction temperature is 0°C-25°C. Alternatively, 0°C-12°C, 12°C-25°C, for example, it can be 0°C, 2°C, 4°C, 6°C, 8°C, 10°C, 12°C, 14°C, 16°C, 18°C, 20°C, 22°C, 24°C or 25°C, but not limited to the listed values, other values not listed in this range are also applicable.

[0052] The equipment material used in the reaction process of the present application can be any material commonly used in chemical manufacturing, and is not particularly limited. However, considering the long-term use of the equipment, the corrosion of the raw materials and the generation of hydrogen fluoride during the hydrolysis of fluorosulfonate, the material is preferably acid and alkali corrosion resistant except glass.

[0053] In the case where the alkali metal salt is used in excess in the reaction step, the excess alkali metal salt remains as an insoluble component. In this case, the method for removing the excess alkali metal salt insoluble component is not particularly limited, and filtration such as reduced pressure filtration, pressure filtration, centrifugal filtration, and the like, and methods such as standing, centrifugal sedimentation, and removal of the supernatant after the standing or centrifugal sedimentation can be used. In addition, these methods can be combined or repeated.

[0054] In the step 1) of the present application, the separation is selected from filtration or centrifugation.

[0055] In the method for producing a fluorosulfonate according to the present application, the step 2) is to concentrate the oil phase obtained in the step 1) to obtain a bisphenol compound; and to concentrate the water phase obtained in the step 2) to obtain a solid, and to add a poor solvent to the solid to purify and crystallize to obtain a fluorosulfonate. The fluorosulfonate such as lithium fluorosulfonate and sodium fluorosulfonate is also applicable to this method.

[0056] In the step 2) of the present application, the method for concentrating the solution of bisfluorosulfonyl bisphenyl ester obtained by separating the reaction solution after the reaction step and completing the reaction is not particularly limited, and can be atmospheric distillation concentration, or reduced pressure distillation concentration, and is preferably reduced pressure distillation concentration at 60°C or lower, and more preferably reduced pressure distillation concentration at 40°C or lower. The lower limit of the vacuum degree is not particularly limited, and in view of the degree to which the actual vacuum degree can be achieved, the lower limit is preferably -0.095 MPa or lower, and further preferably -0.1 MPa or lower; the upper limit of the vacuum degree is not particularly limited, and in view of the finiteness of the measurement of the vacuum degree and the degree to which the actual vacuum system equipment can be achieved, the upper limit is preferably -0.095 MPa or higher, and further preferably -0.096 MPa or higher, and still further preferably -0.098 MPa or higher. Alternatively, the oil phase is concentrated under reduced pressure at a vacuum degree of -0.090 MPa to -0.1 MPa; or -0.090 MPa to -0.95 MPa, or -0.095 MPa to -0.1 MPa. For example, it can be -0.090 MPa, -0.092 MPa, -0.095 MPa, -0.096 MPa, -0.098 MPa, or -0.1 MPa, but is not limited to the listed values, and other values not listed in this range are also applicable.

[0057] In the method for concentrating the water phase obtained by separating the reaction solution after the reaction step and completing the reaction, the reduced pressure distillation concentration is preferably reduced pressure distillation at 80°C or lower, and more preferably reduced pressure distillation at 60°C or lower. The lower limit of the vacuum degree is not particularly limited, and in view of the degree to which the actual vacuum degree can be achieved, it is preferably 5 mmHg to 10 mmHg; the upper limit of the vacuum degree is not particularly limited, and in view of the finiteness of the measurement of the vacuum degree and the degree to which the actual vacuum system equipment can be achieved, it is preferably 5 mmHg or higher, and further preferably 7 mmHg or higher.

[0058] In the step 2) of the present application, a poor solvent is added in the crystallization process, the poor solvent is a poor solvent of the fluorosulfonate, and the poor solvent is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, hydrocarbons, halogenated hydrocarbons, one or more of the hydrocarbons is selected from toluene, n-hexane, n-heptane, petroleum ether, cyclohexane; and the halogenated hydrocarbon is selected from one or more of dichloromethane, dichloroethane, tetrachloroethane, chloroform. Alternatively, the poor solvent is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, toluene, n-hexane, n-heptane, petroleum ether, cyclohexane, dichloromethane, dichloroethane, tetrachloroethane, chloroform.

[0059] Among the above-mentioned solvents, one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dichloromethane, dichloroethane, tetrachloroethane, chloroform and ethyl methyl carbonate is preferred. Among the above-mentioned solvents, one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dichloromethane, dichloroethane, tetrachloroethane and chloroform is further preferred. Among the above-mentioned solvents, one or more of toluene, cyclohexane, dichloromethane, dichloroethane and tetrachloroethane is more preferred.

[0060] The above-mentioned poor solvents can be used alone or in combination. Preferably, the poor solvents are used alone to avoid complicating the operation.

[0061] The poor solvent used in the present application is not particularly limited in the weight ratio relative to the bis-fluorosulfonyl biphenyl ester, and is preferably 30 times or less, more preferably 20 times or less, and further preferably 10 times or less. In addition, the poor solvent used in the crystallization process is preferably 2 times or more, and more preferably 3 times or more, relative to the weight of the bis-fluorosulfonyl biphenyl ester. Within the above-mentioned range, a high yield of crystallization can be ensured, and a good purification effect of crystallization can be ensured, and a fluorosulfonate having good quality and performance can be obtained.

[0062] The temperature at which the poor solvent is added for crystallization in the present application is not particularly limited, and can be selected to be 10°C or less, more preferably 8°C or less, and further preferably 6°C or less. In addition, the temperature at which the poor solvent is added for crystallization can be selected to be 0°C or more, more preferably 3°C or more, and further preferably 5°C or more. Further, in the step 2) of the present application, the crystallization process is dynamic crystallization, and the crystallization temperature is 0°C to 25°C, and can be selected to be 0°C to 10°C or 10°C to 25°C. For example, it can be 0°C, 5°C, 10°C, 15°C, 20°C or 25°C, and is further preferably 0°C to 10°C, but is not limited to the listed values, and other values not listed within the range are also applicable. When the temperature at which the poor solvent is added for crystallization in the present application is within the above-mentioned range, the fluorosulfonate does not precipitate in large amounts due to the low crystallization temperature.

[0063] The feeding time in the poor solvent crystallization process of the present application is not limited, and is preferably 6 hours or less, more preferably 4 hours or less, and further preferably 2 hours or less. In addition, the feeding time in the poor solvent crystallization process of the present application is preferably 1 minute or more, more preferably 10 minutes or more, and further preferably 30 minutes or more. By setting the feeding time in the reaction process of the present application within the above range, a relatively good crystallization purification effect can be obtained with relatively high efficiency.

[0064] The method of solid-liquid separation in the poor solvent crystallization process of the present application is not particularly limited, and filtration methods such as reduced pressure filtration, pressure filtration, and centrifugal filtration can be used to obtain the fluorosulfonate after crystallization.

[0065] The temperature at which solid-liquid separation is performed in the poor solvent crystallization process of the present application is not particularly limited, but in order to improve the crystallization yield, the temperature is preferably 40°C or lower, more preferably 25°C or lower, and further preferably 20°C or lower. On the other hand, if the crystallization yield is excessively increased, there is a risk that the crystallization effect will deteriorate and the quality of the obtained fluorosulfonate will decrease, so the temperature is preferably -20°C or higher, more preferably -10°C or higher, and further preferably 0°C or higher.

[0066] In step 2) of the present application, the crystallized product is filtered and vacuum dried. The fluorosulfonate obtained by the above process has residual organic solvent used in the above process, and thus it is preferable to remove the residual organic solvent by reduced pressure drying. If the temperature is too high, the fluorosulfonate can be thermally decomposed, and if the temperature is too low, the residual organic solvent can not be sufficiently removed. The temperature at which the residual organic solvent is removed is preferably 100°C or lower, more preferably 80°C or lower, and further preferably 60°C or lower. In addition, the temperature is preferably 0°C or higher, more preferably 10°C or higher, and further preferably 20°C or higher. The longer the drying time, the better the removal effect, but the production efficiency can decrease. Alternatively, the drying temperature is 50°C to 100°C, and can be 50°C to 80°C, 80°C to 100°C. For example, the temperature can be 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, but is not limited to the listed values, and other values within the range are also applicable. The drying time is preferably 40 minutes or more, more preferably 1 hour or more, and further preferably 2 hours or more. In addition, the time for which the residual organic solvent is removed by drying is preferably 20 hours or less, more preferably 16 hours or less, and further preferably 12 hours or less.

[0067] The bisphenol compound obtained in step 2) of the present application can be recycled as a raw material for the bisphenol compound in the production method of the bisfluorosulfonyl bisphenyl ester,

[0068] As a preferred technical solution of the present application, the production method includes the following steps:

[0069] (1) mixing the alkali metal salt and the organic solvent, adjusting the temperature to 0-50℃, then adding dropwise the bisfluorosulfonyl bisphenyl ester, after the dropwise addition of the reaction is completed, the reaction is carried out at a temperature of 0-80℃ for 4-12h, after the reaction is completed, the temperature is adjusted to 0-25℃, after filtration or centrifugation, the reaction liquid is obtained; the molar ratio of the cation in the alkali metal salt to the bisfluorosulfonyl bisphenyl ester is (2-6):1, and the mass ratio of the organic solvent to the bisfluorosulfonyl bisphenyl ester is (2-10):1; the structure of the bisfluorosulfonyl bisphenyl ester is as described in the aforementioned formula I.

[0070] The alkali metal salt is selected from any one of lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium methoxide, lithium ethoxide, and lithium isopropoxide; the organic solvent is one or more of dichloromethane, 1,2-dichloroethane, tetrachloroethane, carbon tetrachloride, chloropropane, and acetonitrile.

[0071] The reaction liquid obtained in step (2) is subjected to vacuum concentration at a vacuum degree of -0.090Mpa to -0.1Mpa to obtain the raw material bisphenol compound, after the aqueous phase is concentrated, a poor solvent is added, and the temperature is lowered to 0-25℃ for crystallization, after filtration and drying at 50-100℃, the fluorosulfonate salt is obtained; the poor solvent is a poor solvent of the fluorosulfonate salt, including one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, toluene, n-hexane, n-heptane, petroleum ether, cyclohexane and other hydrocarbons, and dichloromethane, dichloroethane, tetrachloroethane, chloroform and other halogenated hydrocarbons.

[0072] In summary, the present application is simple to operate, the obtained bisphenol compound can be recycled, the generation of three wastes is less, the generation cost is low, the yield and purity of the target product are high, and the production conditions are low, thereby being conducive to large-scale production and application.

[0073] The beneficial effects of the present application are further illustrated by the following examples.

[0074] In order to make the invention purpose, technical scheme and beneficial technical effects of the present application clearer, the present application is further described in detail by combining with the following examples. However, it should be understood that the examples of the present application are only for the purpose of explaining the present application, and are not intended to limit the present application, and the examples of the present application are not limited to the examples given in the specification. The specific experimental conditions or operation conditions in the examples are not specified, and are made according to the conventional conditions or the conditions recommended by the material suppliers.

[0075] Furthermore, it should be understood that the combination of one or more of the method steps mentioned in the present application does not exclude that other method steps can be present before and / or after the mentioned combination of steps or that other method steps can be inserted between two of the explicitly mentioned steps, unless otherwise indicated. It should also be understood that the combination of one or more of the devices / apparatuses mentioned in the present application does not exclude that other devices / apparatuses can be present before and / or after the mentioned combination of devices / apparatuses or that other devices / apparatuses can be inserted between two of the explicitly mentioned devices / apparatuses, unless otherwise indicated. Moreover, the numbering of the method steps only serves as a convenient tool to identify individual method steps in case of multiple method steps and does not intend to have the order of the individual method steps or the order of the individual devices / apparatuses as depicted in the figures to be limiting. The relative placement of the individual method steps or devices / apparatuses can be different in other processes or apparatuses, and the scope of the application should not be interpreted as being limited to the exact sequence of the individual method steps or devices / apparatuses as depicted in the figures, unless otherwise specified.

[0076] In the following examples, the various starting materials of the present application can be commercially available or prepared according to conventional methods in the art, unless otherwise specified.

[0077] Example 1

[0078] The present embodiment provides a lithium fluorosulfonate and a preparation method thereof, the preparation method comprising the following steps: (1) 57 g of bisphenol A, 114 g of dichloromethane and 39.75 g of sodium carbonate are weighed respectively into a 500 mL three-necked flask, stirring is started under ice bath, and the temperature is controlled at 20-25°C, sulfuryl fluoride is started to be introduced, the reaction time is about 8 h, sampling LC control is performed, the raw material is completely reacted, the purity of bisphenol A difluorosulfonate in the reaction solution is more than 98%, the reaction solution is filtered, the filter cake is treated as waste solid, and 212 g of the filtrate is obtained for the next step of hydrolysis;

[0079] (2) 1000 mL of a reaction container is replaced with nitrogen for 3 times, 44.2 g (0.6 mol) of lithium carbonate and 50 g of pure water are sequentially added into the reaction container, the temperature is adjusted to 45°C, and then the filtrate obtained in step (1) is added dropwise, the temperature is controlled at 45-50°C, about 30 min is needed for dropwise addition, 4 h is needed for incubation, the oil phase is taken, LC detection analysis is performed, the raw material is completely reacted, after the reaction is completed, the oil phase with a weight of 171 g and the water phase with a weight of 103 g are separated by standing, the oil phase is concentrated, 57 g of bisphenol A with a purity of 99% is obtained, dichloromethane with a purity of 99% is recovered, both of which are recycled and used, and the reaction formulas of the two steps are as follows:

[0080]

[0081] (3) The 104 g water phase obtained in step (2) is subjected to oil pump decompression to recover pure water, the vacuum degree is controlled at 10 mmHg, and the temperature is controlled at 50-60°C; when the mass of water evaporated is about 50 g, 100 g of ethylene glycol dimethyl ether is added to the remaining material, and dynamic crystallization is carried out at a temperature of 5°C to obtain lithium fluorosulfonate wet product, which is dried at 80°C to obtain 50 g of lithium fluorosulfonate, with a yield of about 94%; after detection, the purity is more than 99%, the sulfate is 35 ppm, the chloride ion is 10 ppm, and the acid value is 36 ppm (calculated based on HF).

[0082] Example 2

[0083] The present embodiment provides a lithium fluorosulfonate and a preparation method thereof, the preparation method comprising the following steps: (1) 57 g of bisphenol A, 114 g of dichloromethane, and 39.75 g of sodium carbonate are weighed into a 500 mL three-necked flask, stirring is started under ice bath cooling, 53.7 g of fluorosulfonic acid chloride is added dropwise, the temperature is controlled at 20-25°C, and the reaction time is about 6 h; sampling LC control shows that the raw material is completely reacted, the purity of bisphenol A difluorosulfonate in the reaction solution is more than 98.5%, the reaction solution is filtered, the filter cake is treated as waste solid, and 212 g of filtrate is obtained for the next step of hydrolysis.

[0084] (2) The 1000 mL reaction container is replaced with nitrogen for 3 times, 44.2 g (0.6 mol) of lithium carbonate and 50 g of pure water are sequentially added to the reaction container, the temperature is adjusted to 45°C, and then the filtrate obtained in step (1) is added dropwise, the temperature is controlled at 45-50°C, and the dropwise addition is completed in about 30 min; after 4 h of incubation, the oil phase is taken, LC detection analysis shows that the raw material is completely reacted, after the reaction is completed, the oil phase is separated by standing, 172 g of oil phase and 104 g of water phase are separated, the oil phase is concentrated to obtain 57 g of bisphenol A with a purity of 99%, and the dichloromethane is recovered with a purity of 99%; both of them are recycled for use. The reaction formulas of the two steps are as follows:

[0085]

[0086] (3) The 104 g water phase obtained in step (2) is subjected to oil pump decompression to recover pure water, the vacuum degree is controlled at 10 mmHg, and the temperature is controlled at 50-60°C; when the mass of water evaporated is about 50 g, 100 g of ethylene glycol dimethyl ether is added to the remaining material, and dynamic crystallization is carried out at a temperature of 5°C to obtain lithium fluorosulfonate wet product, which is dried at 80°C to obtain 50 g of lithium fluorosulfonate, with a yield of about 94%; after detection, the purity is more than 99%, the sulfate is 35 ppm, the chloride ion is 10 ppm, and the acid value is 36 ppm (calculated based on HF).

[0087] Example 3

[0088] The embodiment provides a lithium fluorosulfonate and a preparation method thereof, and the preparation method comprises the following steps: (1) respectively taking 60.5g of bisphenol B, 121g of 1,2-dichloroethane and 31.5g of sodium bicarbonate into a 500ml three-necked flask, starting to pass in sulfuric fluoride under ice bath cooling and starting stirring, temperature control is 20-25 DEG C, reaction time is about 7h, sample LC control is carried out, raw material reaction is complete, the purity of bisphenol A difluorosulfonate in the reaction solution is more than 98.5%, reaction post-treatment is carried out, the reaction solution is filtered, the filter cake is treated as waste solid, and 223g of the filtrate is obtained and used for the next step of hydrolysis.

[0089] The 1000ml reaction container is replaced with nitrogen for three times, 14.4g (0.6mol) of lithium hydroxide, 40g of pure water are sequentially put into the reaction container, temperature is adjusted to 45 DEG C, then the filtrate obtained in step (1) is added dropwise, temperature control is 45-50 DEG C, dropwise addition is completed in about 30min, incubation is carried out for 4h, the oil phase is taken, LC detection analysis is carried out, raw material reaction is complete, after the reaction is completed, standing is carried out, the oil phase 181.5g and the water phase 93g are separated, the oil phase is concentrated, 60.5g of bisphenol B is obtained, the purity is 99%, 1,2-dichloroethane is recovered, the purity is 99%, and both substances are recycled and used.

[0090]

[0091] (3) the 103g of water phase obtained in step (2) is subjected to oil pump decompression, pure water is recovered, vacuum degree control is 10mmHg, temperature control is 50-60 DEG C, when the mass of water vapor is about 40g, 100g of ethylene glycol diethyl ether is added into the remaining material, cooling is carried out to 5 DEG C to carry out dynamic crystallization, filtration is carried out to obtain lithium fluorosulfonate wet product, drying is carried out at 80 DEG C, 48g of lithium fluorosulfonate is obtained, the yield is about 90.5%, detection shows that the purity is more than 99%, the sulfate radical is 40ppm, and the acid value is 33ppm (calculated by HF).

[0092] Example 4

[0093] The embodiment provides a lithium fluorosulfonate and a preparation method thereof, and the preparation method comprises the following steps: (1) respectively taking 60.5g of bisphenol B, 121g of 1,2-dichloroethane and 31.5g of sodium bicarbonate into a 500ml three-necked flask, starting to pass in sulfuric fluoride under ice bath cooling and starting stirring, temperature control is 20-25 DEG C, reaction time is about 7h, sample LC control is carried out, raw material reaction is complete, the purity of bisphenol A difluorosulfonate in the reaction solution is more than 98.5%, reaction post-treatment is carried out, the reaction solution is filtered, the filter cake is treated as waste solid, and 223g of the filtrate is obtained and used for the next step of hydrolysis.

[0094] (2) 1000ml reaction vessel is replaced with nitrogen for 3 times, 23.4g (0.6mol) of lithium methoxide, 50g of pure water are sequentially added into the reaction vessel, the temperature is adjusted to 45℃, then the filtrate obtained in step (1) is added dropwise, the temperature is controlled at 45-50℃, dropwise addition is completed in about 30min, the temperature is kept for 4h, the oil phase is taken, LC detection analysis shows that the raw material is completely reacted, the reaction formula of two steps is as follows, after the reaction is completed, the oil phase 201g and the water phase 108g are separated by standing, the oil phase is concentrated to obtain 67g of bisphenol Z with a purity of 99%, 1,2-dichloroethane with a purity of 99% is recovered, both of which are recycled. The reaction formula of two steps is as follows:

[0095]

[0096] (3) The 108g of water phase obtained in step (2) is subjected to oil pump decompression to recover pure water, the vacuum degree is controlled at 10mmHg, the temperature is controlled at 50-60℃, when the mass of water vapor is about 50g, 100g of ethylene glycol diethyl ether is added into the remaining material, dynamic crystallization is carried out at a temperature of 5℃, lithium fluorosulfonate wet product is obtained by filtration, after drying at 80℃, 49.5g of lithium fluorosulfonate is obtained, the yield is about 93.4%, detection shows that the purity is more than 99%, the sulfate radical is 41ppm, and the acid value is 32ppm (calculated by HF).

[0097] In summary, the present application effectively overcomes the shortcomings in the prior art and has high industrial utilization value.

[0098] The above is only a preferred embodiment of the present application, and is not intended to limit the present application in any form or substance. It should be noted that those skilled in the art can make some improvements and supplements without departing from the method of the present application, and these improvements and supplements should also be considered as the protection scope of the present application. For those skilled in the art, some minor changes, modifications and equivalent changes made by utilizing the technical content disclosed above without departing from the spirit and scope of the present application are equivalent embodiments of the present application; at the same time, any equivalent changes, modifications and evolution of the above-mentioned embodiments made according to the essential technology of the present application are still within the scope of the technical solutions of the present application.

Claims

1. A method for preparing a fluorosulfonate, characterized in that: The preparation method comprises the following steps: 1) mixing bis(fluorosulfonyl)bisphenol phenyl ester, an organic solvent and an alkali metal salt to carry out a hydrolysis reaction, and separating the reaction solution to obtain an aqueous phase and an oil phase; wherein the structure of the bis(fluorosulfonyl)bisphenol phenyl ester is as shown in Formula I, In formula I, R is selected from alkylene, cycloalkylene, aralkylene, arylcycloalkylene, -SO2- or -PO2-; R1 and R2 are independently H, halogen, alkyl, alkoxy or carboxyl; 2) concentrating the oil phase obtained in step 1) to obtain a bisphenol compound; concentrating the aqueous phase obtained in step 1) to obtain a solid, adding a poor solvent to the solid for purification and crystallization to obtain a fluorosulfonate.

2. The method for preparing fluorosulfonate according to claim 1, wherein: In step 1), the preparation method of bisfluorosulfonyl bisphenol phenyl ester comprises: using a bisphenol compound and sulfonyl fluoride as starting materials to prepare bisfluorosulfonyl bisphenol phenyl ester; wherein the structure of the bisphenol compound is as shown in Formula II: In formula II, R is selected from alkylene, cycloalkylene, aralkylene, arcycloalkylene, -SO2- or -PO2-; R1 and R2 are independently H, halogen, alkyl, alkoxy or carboxyl.

3. The method for preparing fluorosulfonate according to claim 2, wherein: Also includes any one or more of the following features: A1) in the preparation method of bisfluorosulfonyl bisphenol phenyl ester, the bisphenol compound is selected from one or more of bisphenol A, bisphenol B, bisphenol C, bisphenol AP, bisphenol E, bisphenol F, bisphenol M, bisphenol S, and bisphenol Z; A2) in the method for preparing bisfluorosulfonyl bisphenol phenyl ester, the sulfonyl fluoride is selected from one or more of sulfuryl fluoride and fluorosulfonyl chloride; A3) The method for preparing bisfluorosulfonyl bisphenol phenyl ester further comprises a solvent selected from one or more of dichloromethane, 1,2-dichloroethane, tetrachloroethane, carbon tetrachloride, and acetonitrile; A4) In the method for preparing bisfluorosulfonyl bisphenol phenyl ester, the molar ratio of the bisphenol compound to the sulfonyl fluoride reagent is 1:(2.0-2.3); A5) The method for preparing bisfluorosulfonyl bisphenol phenyl ester further comprises an acid binding agent selected from one or more of sodium carbonate, sodium bicarbonate, triethylamine, pyridine, and ethylenediamine; the molar ratio of the acid binding agent to the bisphenol compound is (2.1-2.5):1; A6) In the preparation method of bis(fluorosulfonyl)bisphenol phenyl ester, the reaction temperature is room temperature; A7) In the preparation method of bisfluorosulfonyl bisphenol phenyl ester, the reaction time is 6 h to 8 h.

4. The method for preparing fluorosulfonate according to claim 3, wherein: In feature A2), sulfuryl fluoride is passed into an acetonitrile solution of the bisphenol compound, or fluorosulfonyl chloride is added dropwise.

5. The method for preparing fluorosulfonate according to claim 1, wherein: Also includes any one or more of the following conditions: B1) in step 1), the alkali metal salt is selected from one or more of alkali metal carbonates, alkali metal bicarbonates, alkali metal oxides, alkali metal hydroxides or alkali metal alcoholates; B2) in step 1), the organic solvent is selected from one or more of dichloromethane, 1,2-dichloroethane, tetrachloroethane, carbon tetrachloride, chloropropane, chlorobenzene, p-dichlorobenzene, and acetonitrile; B3) in step 1), the molar ratio of the cation in the alkali metal salt to the bis(fluorosulfonyl)bisphenol phenyl ester is (2-6):1; B4) in step 1), the mass ratio of the organic solvent to bis(fluorosulfonyl)bisphenol phenyl ester is (3-10):1; B5) Step 1) further comprises using water during hydrolysis, wherein the mass ratio of water to bis(fluorosulfonyl)bisphenol phenyl ester is 1:(2-3).

6. The method for preparing fluorosulfonate according to claim 1, wherein: Also includes any one or more of the following conditions: B11) in step 1), the alkali metal carbonate is selected from one or more of lithium carbonate and lithium bicarbonate; B12) in step 1), the alkali metal oxide is lithium oxide; B13) in step 1), the alkali metal hydroxide is lithium hydroxide; B14) in step 1), the alkali metal alcoholate is selected from one or more of lithium methoxide, lithium ethoxide, lithium isopropoxide, and lithium tert-butoxide; B31) In step 1), the cation in the alkali metal salt is a lithium ion.

7. The method for preparing fluorosulfonate according to claim 1, wherein: Also includes any one or more of the following conditions: C1) the reaction temperature in step 1) is 20°C to 50°C; the reaction time is 4h to 12h; C2) the reaction end temperature of step 1) is 0°C to 25°C; C3) In step 1), separation is selected from filtration or centrifugation.

8. The method for preparing fluorosulfonate according to claim 1, wherein: In step 2), the poor solvent is a poor solvent for fluorosulfonate, and the poor solvent is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, toluene, n-hexane, n-heptane, petroleum ether, cyclohexane, dichloromethane, dichloroethane, tetrachloroethane, and chloroform.

9. The method for preparing fluorosulfonate according to claim 8, wherein: In step 2), the poor solvent is selected from one or more of toluene, cyclohexane, dichloromethane, dichloroethane, and tetrachloroethane.

10. The method for preparing fluorosulfonate according to claim 1, wherein: Also includes any one or more of the following conditions: D1) in step 2), the oil phase is concentrated under reduced pressure, with a vacuum degree of -0.090 MPa to -0.1 MPa; D2) in step 2), the aqueous phase is concentrated by vacuum distillation with a vacuum degree of 5 mmHg to 10 mmHg; D3) in step 2), the crystallization process is dynamic crystallization, and the crystallization temperature is 0°C to 25°C; D4) In step 2), after crystallization, filtering and vacuum drying are performed; the drying temperature is 50° C. to 100° C.

11. The method for preparing fluorosulfonate according to claim 2, wherein: The bisphenol compound obtained in step 2) can be recycled into the preparation method of bisfluorosulfonyl bisphenol phenyl ester and used as a bisphenol compound raw material.

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