Preparation method of fluoroethylene sulfate

Abstract

The invention discloses a preparation method of fluoroethylene sulfate, an electrolyte, a battery and a power utilization device. Belongs to the technical field of ester preparation methods, and the preparation method of fluoroethylene sulfate comprises the following steps: mixing ethylene sulfate and sulfonyl chloride, heating, and reacting to obtain chloroethylene sulfate; and mixing the chloroethylene sulfate solution with metal fluoride, heating, and reacting to obtain the fluoroethylene sulfate. According to the method, sulfonyl chloride is used as a chlorination reagent and reacts with ethylene sulfate to synthesize chloroethylene sulfate, and then the chloroethylene sulfate is used for synthesizing the fluoroethylene sulfate. Firstly, sulfonyl chloride is low in price, convenient to use and non-toxic, is a reaction raw material and can also serve as a solvent, a new solvent does not need to be additionally introduced, post-treatment is simple and convenient, the synthesis process is simple, and reaction conditions are milder.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of batteries, in particular to a preparation method of fluoroethylene sulfate. BACKGROUND

[0002] Fluoroethylene sulfate is a commonly used lithium battery electrolyte additive, which can significantly improve the specific capacity of the battery, improve the safety and service life of the battery, and improve the charge-discharge performance and cycle performance of the battery.

[0003] At present, the method for synthesizing fluoroethylene sulfate mainly uses fluoroethylene sulfate to synthesize halogenated fluoroethylene sulfate, and then uses a fluorinating agent to obtain fluoroethylene sulfate. The main halogenating agent for synthesizing halogenated fluoroethylene sulfate is N-bromosuccinimide, N-chlorosuccinimide, and chlorine, which has the defects of high price, high toxicity, introduction of new solvents, long reaction time, and high reaction temperature. SUMMARY

[0004] The present application is carried out in view of the above-mentioned problems, and aims to provide a preparation method of fluoroethylene sulfate, which reduces cost, reduces toxicity, and makes the reaction conditions more mild.

[0005] In order to achieve the above-mentioned purpose, the present application provides a preparation method of fluoroethylene sulfate, an electrolyte, a battery and an electric device.

[0006] In a first aspect, the present application provides a preparation method of fluoroethylene sulfate, comprising the following steps:

[0007] Mixing fluoroethylene sulfate and sulfuryl chloride, heating, and reacting to obtain chloroethylene sulfate;

[0008] Mixing a solution of chloroethylene sulfate and metal fluoride, heating, and reacting to obtain fluoroethylene sulfate.

[0009] Therefore, in the technical scheme of the present application, sulfuryl chloride is used as a chlorinating agent to react with fluoroethylene sulfate to synthesize chloroethylene sulfate, and then chloroethylene sulfate is used to synthesize fluoroethylene sulfate. First, sulfuryl chloride is inexpensive, easy to use, and non-toxic. It is not only a reaction raw material, but also can act as a solvent, without the need to introduce new solvents, the post-treatment is simple and convenient, the synthesis process is simple, and the reaction conditions are more mild. The reaction principle of sulfuryl chloride and fluoroethylene sulfate is that sulfuryl chloride is covalently cleaved to form chlorine radicals under heating conditions, and substitution reaction occurs with fluoroethylene sulfate to form chloroethylene sulfate. The reaction general formula is:

[0010]

[0011] In any embodiment, in the step of "mixing vinyl sulfate and sulfuryl chloride, heating, and reacting to obtain chloro vinyl sulfate", the mass ratio of vinyl sulfate to sulfuryl chloride is 1:(1.5-20). With this mass ratio, the yield of chloro vinyl sulfate can be improved, and the more expensive vinyl sulfate can be used as much as possible, and the less expensive sulfuryl chloride can be used as both a raw material and a solvent, thereby reducing the cost.

[0012] In any embodiment, the mass ratio of vinyl sulfate to sulfuryl chloride is 1:(3-5). With this mass ratio, the yield of chloro vinyl sulfate can be improved, and the difficulty of recovering sulfuryl chloride can be reduced, thereby reducing the cost, pollution, and waste.

[0013] In any embodiment, in the step of "mixing vinyl sulfate and sulfuryl chloride, heating, and reacting to obtain chloro vinyl sulfate", the heating temperature is 40-90°C. With this reaction temperature, the reaction can be carried out sufficiently, the reaction rate of chloro vinyl sulfate can be improved, and the reaction conditions can be made milder, thereby reducing the occurrence of side reactions and improving the yield of chloro vinyl sulfate.

[0014] In any embodiment, in the step of "mixing vinyl sulfate and sulfuryl chloride, heating, and reacting to obtain chloro vinyl sulfate", the heating temperature is 50-70°C. With this reaction temperature, the reaction can be carried out sufficiently, the reaction rate of chloro vinyl sulfate can be improved, and the reaction conditions can be made milder, thereby reducing the occurrence of side reactions and improving the yield of chloro vinyl sulfate.

[0015] In any embodiment, the step of "mixing vinyl sulfate and sulfuryl chloride, heating, and reacting to obtain chloro vinyl sulfate" comprises mixing vinyl sulfate and sulfuryl chloride, heating, and adding a free radical initiator to the reaction system in batches during heating to obtain chloro vinyl sulfate. By adding a free radical initiator to the reaction system in batches during heating, the reaction efficiency can be improved, and the yield of chloro vinyl sulfate can be improved. The principle is that the free radical initiator can form free radicals by breaking, and can activate vinyl sulfate to promote the substitution reaction of sulfuryl chloride to produce chloro vinyl sulfate.

[0016] In any embodiment, the free radical initiator comprises at least one of azobisisobutyronitrile and azobisisoheptyl nitrile. The above free radical is an azo initiator, which is a free radical initiator containing a nitrogen-nitrogen double bond in the molecular structure. By using at least one of the above free radical initiators, the free radicals can be more easily broken, and the activation effect is better.

[0017] In any embodiment, the molar ratio of the free radical initiator to the vinyl sulfate is (0.1-5): 100. At this mass ratio, the yield of vinyl chlorosulfate can be increased while reducing the amount of the free radical initiator, saving costs and reducing the occurrence of side reactions.

[0018] In any embodiment, the molar ratio of the free radical initiator to the vinyl sulfate is (0.5-2):100. This can further improve the yield of vinyl chlorosulfate while reducing the amount of the free radical initiator, saving costs. It can also lower the reaction temperature, shorten the reaction time, and reduce the occurrence of side reactions.

[0019] In any embodiment, in the step of "mixing a solution of vinyl chlorosulfate with a metal fluoride, heating, and reacting to obtain vinyl fluorosulfate":

[0020] The mass ratio of the metal fluoride to the vinyl chlorosulfate is (1-10):1; at this mass ratio, the yield of vinyl fluorosulfate can be increased, the waste of raw materials can be reduced, and the cost can be reduced. And / or,

[0021] The metal fluoride includes at least one of potassium fluoride, sodium fluoride, cesium fluoride, antimony trifluoride and antimony pentafluoride; using at least one of the above metal fluorides can increase the reaction rate, increase the yield of fluoroethylene sulfate, and reduce costs. And / or,

[0022] The solution of vinyl chlorosulfate contains at least one of triethylene glycol and tetraethylene glycol as solvents. Using at least one of the above solvents can effectively dissolve the metal fluoride and simultaneously make the reaction temperature reach the heating temperature, thereby promoting the fluorination reaction.

[0023] The heating temperature is 80-150° C. At this heating temperature, the reaction rate can be increased, the yield of vinyl fluorosulfate can be increased, and the reaction conditions can be milder, thereby reducing costs.

[0024] In any embodiment, the step of "mixing a solution of vinyl chlorosulfate with a metal fluoride, heating, and reacting to obtain vinyl fluorosulfate" comprises: mixing a solution of vinyl chlorosulfate with a metal fluoride and a catalyst, heating, and reacting to obtain vinyl fluorosulfate. Adding a catalyst to the reaction system of the vinyl chlorosulfate solution and the metal fluoride can increase the reaction rate and the yield of vinyl fluorosulfate.

[0025] In any embodiment, the catalyst includes at least one of potassium iodide, sodium iodide, potassium bromide, and sodium bromide. The at least one of the above catalysts is selected to facilitate the more easy departure of fluoride ion from the metal fluoride, to increase the reaction speed, to increase the yield of the fluoroethylene sulfate, and to reduce the occurrence of side reactions.

[0026] In any embodiment, the catalyst is in a mass ratio of (0.1-2): 100 with respect to the chloroethylene sulfate. At this mass ratio, the efficiency of the reaction can be increased, the yield of the fluoroethylene sulfate can be increased, and the occurrence of side reactions can be reduced. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 is a gas chromatogram of the fluoroethylene sulfate prepared by the preparation method of the fluoroethylene sulfate of Example 3 of the present application.

[0028] Figure 2 is a gas chromatogram of the fluoroethylene sulfate prepared by the preparation method of the fluoroethylene sulfate of Example 3 of the present application. DETAILED DESCRIPTION

[0029] Hereinafter, embodiments of the preparation method of the fluoroethylene sulfate of the present application are specifically disclosed. However, there are cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of matters that are already well known, repeated descriptions of actually identical structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. In addition, the drawings and the following description are provided so that those skilled in the art can fully understand the present application, and are not intended to limit the subject matter recited in the claims.

[0030] The ranges disclosed herein are intended to be "open" ranges, i.e., the upper and lower limits of the range are not included. The ranges are also intended to include any and all sub-ranges of the same, wherein each sub-range is inclusive of the end values. For example, if a range is from 1 to 10, then the range includes any and all sub-ranges between (and including) the minimum of 1 and the maximum of 10, that is, any of 1 to 3, 4 to 6, 5 to 7, 3 to 10, 8 to 10, 1 to 10, etc. Also, it is specifically intended that the minimum and maximum values of the ranges are included in the ranges. For example, if a parameter is 2 to 5, it is intended that the parameter can be 2, 3, 4, or 5, and the parameter is also intended to be 2 to 5, i.e., 2, 3, 4, and 5 are included in the range.

[0031] All embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions, if not specifically stated otherwise.

[0032] All technical features and optional technical features of the present application can be combined with each other to form new technical solutions, if not specifically stated otherwise.

[0033] All steps of the present application can be performed in sequence or randomly, preferably in sequence, if not specifically stated otherwise. For example, the method comprises steps (a) and (b) means that the method can comprise steps (a) and (b) in sequence, or steps (b) and (a) in sequence. For example, the method can further comprise step (c) means that step (c) can be added to the method in any sequence, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0034] Vinyl fluoride sulfates are commonly used lithium battery electrolyte additives, which can significantly improve the specific capacity of the battery, improve the safety and service life of the battery, and improve the charge-discharge performance and cycle performance of the battery.

[0035] The current method for synthesizing fluoro vinyl sulfate mainly uses vinyl sulfate to synthesize halogenated vinyl sulfate, and then uses a fluorinating agent to obtain fluoro vinyl sulfate. The main halogenating agent for synthesizing halogenated vinyl sulfate is N-bromosuccinimide, N-chlorosuccinimide, and chlorine, which has the defects of high price, high toxicity, introduction of new solvents, long reaction time, and high reaction temperature.

[0036] Surprisingly, by using sulfuryl chloride as a chlorinating agent to react with vinyl sulfate to synthesize chloro vinyl sulfate, and then using chloro vinyl sulfate to synthesize fluoro vinyl sulfate, the cost is reduced, the toxicity is reduced, and the reaction conditions are more mild.

[0037] Based on this, the application provides a preparation method of fluoro vinyl sulfate.

[0038] In a first aspect, the embodiments of the application provide a preparation method of fluoro vinyl sulfate, comprising the following steps:

[0039] Mixing vinyl sulfate and sulfuryl chloride, heating, and reacting to obtain chloro vinyl sulfate;

[0040] Mixing a solution of chloro vinyl sulfate with metal fluoride, heating, and reacting to obtain fluoro vinyl sulfate.

[0041] In the technical solution of the embodiments of the application, by using sulfuryl chloride as a chlorinating agent to react with vinyl sulfate to synthesize chloro vinyl sulfate, and then using chloro vinyl sulfate to synthesize fluoro vinyl sulfate. First, sulfuryl chloride is cheap, easy to use, and non-toxic. It is not only a reaction raw material, but also can act as a solvent, without the need to introduce new solvents, and the post-processing is simple and convenient. The synthesis process is simple, and the reaction conditions are more mild. The reaction principle of using sulfuryl chloride to react with vinyl sulfate is that sulfuryl chloride is covalently cleaved to form chlorine radicals under heating conditions, and substitution reaction occurs with vinyl sulfate to form chloro vinyl sulfate. The general reaction formula is:

[0042]

[0043] In any embodiment, in the step of "mixing vinyl sulfate and sulfuryl chloride, heating, and reacting to obtain chloro vinyl sulfate", the mass ratio of vinyl sulfate to sulfuryl chloride is 1:(1.5-20). Under this mass ratio, the yield of chloro vinyl sulfate can be improved, and the cost of the more expensive vinyl sulfate is as high as possible. The low-cost sulfuryl chloride is used as a reaction raw material and a solvent to reduce the cost. The mass ratio of vinyl sulfate to sulfuryl chloride can be 1:1.5, 1:2, 1:3, 1:4, 1:5, 1:10, 1:15, or 1:20.

[0044] In any embodiment, the molar ratio of vinyl sulfate and sulfonyl chloride is 1:(3-5). The yield of chlorovinyl sulfate is improved, the recovery of sulfonyl chloride is reduced, the cost is lowered, the pollution and waste are reduced.

[0045] In any embodiment, the temperature of heating in the step of mixing vinyl sulfate and sulfonyl chloride, heating, and reacting to obtain chlorovinyl sulfate is 40-90℃. At this reaction temperature, on the one hand, the reaction can be carried out sufficiently, the reaction rate of chlorovinyl sulfate is improved, and on the other hand, the reaction condition can be more moderate, the occurrence of side reactions is reduced, and the yield of chlorovinyl sulfate is improved. The temperature of heating can be 40℃, 50℃, 60℃, 70℃, 80℃, or 90℃.

[0046] In any embodiment, the temperature of heating in the step of mixing vinyl sulfate and sulfonyl chloride, heating, and reacting to obtain chlorovinyl sulfate is 50-70℃. The reaction can be carried out further sufficiently, the reaction rate of chlorovinyl sulfate is improved, and the reaction condition can be more moderate, the occurrence of side reactions is reduced, and the yield of chlorovinyl sulfate is improved.

[0047] In any embodiment, the step of mixing vinyl sulfate and sulfonyl chloride, heating, and reacting to obtain chlorovinyl sulfate comprises: mixing vinyl sulfate and sulfonyl chloride, heating, and adding free radical initiator into the reaction system in batches during heating to obtain chlorovinyl sulfate. By adding free radical initiator into the reaction system in batches during heating, the efficiency of the reaction can be improved, and the yield of chlorovinyl sulfate is improved. The principle is that free radical initiator can break to form free radicals, and can activate vinyl sulfate to promote the substitution reaction of sulfonyl chloride to produce chlorovinyl sulfate. Adding free radical initiator in batches can avoid too strong reaction, reduce the occurrence of side reactions, and improve the yield of chlorovinyl sulfate.

[0048] In any embodiment, the free radical initiator comprises at least one of azobisisobutyronitrile and azobisisoheptyl nitrile. The above-mentioned free radical initiator is an azo initiator, which is a free radical initiator containing a nitrogen-nitrogen double bond in the molecular structure. Using at least one of the above-mentioned free radical initiators can break more easily to form free radicals, and the activation effect is better. The mechanism of action is that azo initiator is decomposed into isobutyronitrile (or heptyl nitrile) group at 40-80℃ or above, thereby initiating free radical reaction. Azo initiator can be decomposed into three parts: nitrogen, carbon, and hydrogen. Nitrogen can form a hydrophobic active group to assist the transfer of free radicals in the reaction; carbon can combine with free radicals to form an active group to form a stable transition state; hydrogen can provide hydrogen atoms to the reactants to assist the completion of the reaction of the reactants.

[0049] In any embodiment, the molar ratio of the radical initiator to the ethylene sulfate is (0.1-5): 100. At this mass ratio, the use of the radical initiator can be reduced on the basis of improving the yield of chloro ethylene sulfate, saving cost, and reducing the occurrence of side reactions. The molar ratio of the radical initiator to the ethylene sulfate can be 0.1: 100, 0.5: 100, 1: 100, 2: 100, 3: 100, 4: 100, or 5: 100.

[0050] In any embodiment, the molar ratio of the radical initiator to the ethylene sulfate is (0.5-2): 100. The use of the radical initiator can be further reduced on the basis of improving the yield of chloro ethylene sulfate, saving cost, reducing the reaction temperature, shortening the reaction time, and reducing the occurrence of side reactions.

[0051] In any embodiment, in the step of mixing the solution of chloro ethylene sulfate with metal fluoride, heating, and reacting to obtain fluoro ethylene sulfate: the molar ratio of the metal fluoride to the chloro ethylene sulfate is (1-10): 1. At this mass ratio, the yield of fluoro ethylene sulfate can be improved, raw material waste can be reduced, and cost can be lowered. The molar ratio of the metal fluoride to the chloro ethylene sulfate can be 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, or 10: 1.

[0052] In any embodiment, in the step of mixing the solution of chloro ethylene sulfate with metal fluoride, heating, and reacting to obtain fluoro ethylene sulfate: the metal fluoride includes at least one of potassium fluoride, sodium fluoride, cesium fluoride, antimony trifluoride, and antimony pentafluoride. The use of at least one of the above metal fluorides can improve the reaction rate, improve the yield of fluoro ethylene sulfate, and lower the cost.

[0053] In any embodiment, in the step of mixing the solution of chloro ethylene sulfate with metal fluoride, heating, and reacting to obtain fluoro ethylene sulfate: the solvent in the solution of chloro ethylene sulfate includes at least one of triethylene glycol and tetraethylene glycol. The use of at least one of the above solvents can effectively dissolve the metal fluoride, and the reaction temperature can reach the heating temperature, promoting the fluorination reaction to proceed.

[0054] In any embodiment, in the step of "mixing the solution of chloro vinyl sulfate with metal fluoride, heating, and reacting to obtain fluoro vinyl sulfate", the heating temperature is 80-150°C. At this heating temperature, the reaction rate can be increased, the yield of fluoro vinyl sulfate can be increased, and the reaction condition can be more mild, and the cost can be reduced. The heating temperature can be 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C.

[0055] In any embodiment, the step of "mixing the solution of chloro vinyl sulfate with metal fluoride, heating, and reacting to obtain fluoro vinyl sulfate" comprises mixing the solution of chloro vinyl sulfate with metal fluoride and a catalyst, heating, and reacting to obtain fluoro vinyl sulfate. The addition of a catalyst to the reaction system of the solution of chloro vinyl sulfate and metal fluoride can increase the reaction rate, and increase the yield of fluoro vinyl sulfate.

[0056] In any embodiment, the catalyst comprises at least one of potassium iodide, sodium iodide, potassium bromide, and sodium bromide. At least one of the above catalysts is selected to facilitate the easier departure of fluoride ions from the metal fluoride, increase the reaction rate, increase the yield of fluoro vinyl sulfate, and reduce the occurrence of side reactions.

[0057] In any embodiment, the mass ratio of the catalyst to the chloro vinyl sulfate is (0.1-2):100. At this mass ratio, the reaction efficiency can be increased, the yield of fluoro vinyl sulfate can be increased, and the occurrence of side reactions can be reduced. The mass ratio of the catalyst to the chloro vinyl sulfate can be 0.1:100, 0.5:100, 1:100, 1.5:100, or 2:100.

[0058] The technical solutions of the present application are further described in detail below in combination with specific examples. It should be understood that the following examples are only used to explain the present application and do not limit the present application.

[0059] Example 1

[0060] A method for preparing fluoro vinyl sulfate comprises the following steps:

[0061] Vinyl sulfate and sulfuryl chloride are mixed at a mass ratio of 1:2.5, heated at 60°C, and reacted for 8h to obtain chloro vinyl sulfate, and the chloro vinyl sulfate is obtained by rectification;

[0062] The triethylene glycol solution of chloro vinyl sulfate is mixed with potassium fluoride, the mass ratio of chloro vinyl sulfate to potassium fluoride is 1:3, heated at 150℃, the reaction is carried out for 5h, after the reaction is completed, the solid is removed by filtration, the liquid is concentrated, recrystallized by using dichloromethane, and vinyl fluoride sulfate is obtained. The yield of vinyl fluoride sulfate is 9%, and the purity is 99.1%.

[0063] Example 2

[0064] A method for preparing vinyl fluoride sulfate comprises the following steps:

[0065] The vinyl sulfate and the sulfonyl chloride are mixed in a mass ratio of 1:2.5, heated at 60℃, and azobisisobutyronitrile is added to the reaction system in batches during the heating process, the mass ratio of azobisisobutyronitrile to vinyl sulfate is 1.5:100, the reaction is carried out for 8h, and chloro vinyl sulfate is obtained;

[0066] The triethylene glycol solution of chloro vinyl sulfate is mixed with potassium fluoride, the mass ratio of chloro vinyl sulfate to potassium fluoride is 1:3, heated at 150℃, the reaction is carried out for 5h, after the reaction is completed, the solid is removed by filtration, the liquid is concentrated, recrystallized by using dichloromethane, and vinyl fluoride sulfate is obtained. The yield of vinyl fluoride sulfate is 9%, and the purity is 99.1%.

[0067] Example 3

[0068] A method for preparing vinyl fluoride sulfate comprises the following steps:

[0069] The vinyl sulfate and the sulfonyl chloride are mixed in a mass ratio of 1:2.5, heated at 60℃, and azobisisobutyronitrile is added to the reaction system in batches during the heating process, the mass ratio of azobisisobutyronitrile to vinyl sulfate is 1:1, the reaction is carried out for 8h, and chloro vinyl sulfate is obtained;

[0070] The triethylene glycol solution of chloro vinyl sulfate is mixed with potassium fluoride and potassium iodide, the mass ratio of chloro vinyl sulfate to potassium fluoride is 1:3, the mass ratio of chloro vinyl sulfate to potassium iodide is 100:0.5, heated at 80℃, the reaction is carried out for 5h, after the reaction is completed, the solid is removed by filtration, the liquid is concentrated, recrystallized by using dichloromethane, and vinyl fluoride sulfate is obtained. The yield of vinyl fluoride sulfate is 80.9%, and the purity is 99.6%.

[0071] The parameters of examples 4 to 19 of the present application are shown in table 1.

[0072] Table 1: Parameters of the method for preparing vinyl fluoride sulfate in examples 4 to 19

[0073]

[0074]

[0075] Performance test

[0076] The product purity and product yield of the fluoro vinyl sulfate prepared in statistical examples 1 to 19 were tested, wherein the product purity was measured by gas chromatograph, the product yield = actual amount of target product generated / theoretical amount of target product generated x 100%, and the results are shown in Table 1. The intermediate chloro vinyl sulfate prepared in example 3 and the product fluoro vinyl sulfate prepared were subjected to gas phase mass spectrometry detection, and the spectra are shown in Figure 1 and Figure 2 .

[0077] The test conditions for purity are as follows:

[0078] Device model: 8890-5977B, brand: Agilent;

[0079] Injection amount: 0.8ul, split ratio: 10:1;

[0080] Injection port temperature: 280℃;

[0081] Programmed temperature method: 50℃ for 1min, increased to 280℃ at a rate of 15℃ / min, and maintained for 10min;

[0082] Column flow rate: 1ml / min;

[0083] Chromatographic column model: HP-5MS UI, size: 30m x 250um x 0.25um;

[0084] MSD transfer line temperature: 280℃;

[0085] Scan range: 5-700m / z;

[0086] As can be seen from Figure 1 , the out-of-peak and ion fragment peaks of the compound obtained in the first step reaction in GC-MS can determine the molecular weight (158 / 160 = 3:1) and ion fragments of the compound, which are consistent with the molecular weight and ion fragments of the product, and it can be determined that the compound is chloro vinyl sulfate.

[0087] As can be seen from Figure 2 , the out-of-peak and ion fragment peaks of the product obtained in the reaction in GC-MS can determine the molecular weight 142 and ion fragments of the compound, which are consistent with the molecular weight and ion fragments of the product, and it can be determined that the compound is fluoro vinyl sulfate.

[0088] In summary, by using sulfonyl chloride as chlorinating reagent, ethylene sulfate chlorides are synthesized by reacting with ethylene sulfate, and then fluoroethylene sulfate is synthesized by using ethylene sulfate chlorides. Firstly, sulfonyl chloride is cheap, convenient to use, non-toxic, which is not only a reaction raw material, but also can act as a solvent, without additional introduction of new solvents, and the post-treatment is simple and convenient. The synthesis process is simple, and the reaction condition is more mild.

[0089] The above merely describes preferred embodiments of the present application, and does not limit the patent scope of the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application shall be included in the patent protection scope of the present application.

Claims

1. A process for the preparation of ethylene fluorosulfate, characterized in that, The method comprises the following steps: The step of mixing vinyl sulfate and sulfonyl chloride, heating, and reacting to obtain chloro vinyl sulfate; The step of mixing a solution of chloro vinyl sulfate and metal fluoride, heating, and reacting to obtain fluoro vinyl sulfate.

2. The method for preparing vinyl fluorosulfate according to claim 1, wherein In the step of mixing vinyl sulfate and sulfonyl chloride, heating, and reacting to obtain chloro vinyl sulfate: The molar ratio of vinyl sulfate to sulfonyl chloride is 1:(1.5-20).

3. The method for preparing vinyl fluorosulfate according to claim 2, wherein The molar ratio of vinyl sulfate to sulfonyl chloride is 1:(3-5).

4. The process for the preparation of ethylene fluorosulfate according to any one of claims 1 to 3, characterized in that, In the step of mixing vinyl sulfate and sulfonyl chloride, heating, and reacting to obtain chloro vinyl sulfate, the heating temperature is 40-90°C.

5. The method for preparing vinyl fluorosulfate according to claim 4, wherein In the step of mixing vinyl sulfate and sulfonyl chloride, heating, and reacting to obtain chloro vinyl sulfate, the heating temperature is 50-70°C.

6. The process for preparing ethylene fluorosulfate according to any one of claims 1 to 5, characterized in that, The step of mixing vinyl sulfate and sulfonyl chloride, heating, and reacting to obtain chloro vinyl sulfate comprises: The step of mixing vinyl sulfate and sulfonyl chloride, heating, and reacting to obtain chloro vinyl sulfate comprises adding a free radical initiator to the reaction system in batches during heating.

7. The method for preparing vinyl fluorosulfate according to claim 6, wherein The free radical initiator comprises at least one of azobisisobutyronitrile and azobisisoheptyl nitrile.

8. The process for the preparation of ethylene fluorosulfate according to claim 6 or 7, characterized in that, The molar ratio of the free radical initiator to the vinyl sulfate is (0.1-5):

100.

9. The method for preparing vinyl fluorosulfate according to claim 8, wherein The molar ratio of the free radical initiator to the vinyl sulfate is (0.5-2):

100.

10. The process for the preparation of ethylene fluorosulfate according to any one of claims 1 to 9, characterized in that, In the step of mixing a solution of chloro vinyl sulfate and metal fluoride, heating, and reacting to obtain fluoro vinyl sulfate: The molar ratio of the metal fluoride to the chloro vinyl sulfate is (1-10):1; and / or, The metal fluoride comprises at least one of potassium fluoride, sodium fluoride, cesium fluoride, antimony trifluoride, and antimony pentafluoride; and / or, The solvent in the solution of chloro vinyl sulfate comprises at least one of triethylene glycol and tetraethylene glycol; and / or, The heating temperature is 80-150°C.

11. The process for the preparation of ethylene fluorosulfate according to any one of claims 1 to 10, characterized in that, The step of mixing a solution of chloro vinyl sulfate and metal fluoride, heating, and reacting to obtain fluoro vinyl sulfate comprises: The step of mixing a solution of chloro vinyl sulfate and metal fluoride, heating, and reacting to obtain fluoro vinyl sulfate comprises mixing the solution of chloro vinyl sulfate, metal fluoride, and a catalyst, heating, and reacting to obtain fluoro vinyl sulfate.

12. The method for preparing vinyl fluorosulfate according to claim 11, wherein The catalyst comprises at least one of potassium iodide, sodium iodide, potassium bromide, and sodium bromide.

13. The process for the preparation of ethylene fluorosulfate according to claim 11 or 12, characterized in that, The molar ratio of the catalyst to the chloro vinyl sulfate is (0.1-2):100.

Images