Process for the preparation of sulfonyl fluorides

Abstract

The present application relates to a method for preparing sulfuryl fluoride, the method comprising: (1) providing a reaction stream comprising an organic base-hydrogen fluoride complex; (2) introducing sulfur dioxide and chlorine into the reaction stream comprising the organic base-hydrogen fluoride complex, and reacting to form a product stream comprising sulfuryl fluoride. The method described in the present application has mild reaction conditions, high product yield and purity, material recycling, less waste, etc., and is suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of chemical product production, in particular to a preparation method of sulfuryl fluoride. BACKGROUND

[0002] Sulfuryl fluoride is an inorganic compound with the chemical formula SO2F2, which is a colorless and odorless toxic gas at normal temperature and pressure. Due to its strong diffusion and penetration, broad-spectrum insecticidal, low dosage, low residual, fast insecticidal speed, short gas dispersion time, convenient use at low temperature, no effect on germination rate and low toxicity, sulfuryl fluoride is more and more widely used in warehouse, cargo ship, container and building, reservoir dam, termite control and garden overwintering pest and live tree boring pest control.

[0003] In recent years, with the development of the lithium battery industry, sulfuryl fluoride has also been widely used in the synthesis of electrolyte lithium salt lithium bisfluorosulfonylimide. LiFSI has excellent performance and is more suitable for fast charging, high endurance and other needs. Compared with LiPF6, LiFSI is more excellent in electrolyte conductivity, high and low temperature performance, thermal stability, hydrolysis resistance and gas expansion inhibition, and is therefore considered as the most promising lithium salt to replace LiPF6.

[0004] The currently reported synthesis methods of sulfuryl fluoride include:

[0005] 1. Preparation by fluorination of sulfuryl chloride as raw material

[0006] US7145046 discloses the preparation of sulfuryl fluoride with fluoride of organic base. Synthesis of Fluorides by Metathesis with Sodium Fluoride (J.O.C 1965, 25, 2016) and Indian Journal of Chemistry 1981 (Vol. 20A, pp. 777-779) report the preparation of sulfuryl fluoride with potassium fluoride, sodium fluoride and the like as fluoride.

[0007] CN202210110583.8 discloses that the complex of sulfuryl chloride and hydrogen fluoride reacts under certain conditions to prepare sulfuryl fluoride, but the preparation process needs to control the temperature of the hydrogen fluoride complex to be lower than 10℃ in advance to prevent boiling. More importantly, the sulfuryl chloride used in this preparation method needs dry sulfur dioxide and chlorine gas to react at high temperature in the presence of a catalyst such as activated carbon, camphor and the like.

[0008] 2. Preparation by fluorination of sulfur trioxide as raw material

[0009] US3403144 discloses the preparation of sulfuryl fluoride by fluorination of sulfur trioxide and barium fluoride or barium fluorosilicate as raw materials at a high temperature of 500-600℃.

[0010] 3. Preparation of sulfuryl fluoride from compounds of hexavalent sulfur by fluorination of different fluorides

[0011] The methods generally have harsh reaction conditions, such as high temperature reaction using sulfur trioxide as a raw material or too violent reaction (such as strong exothermic using sulfuryl chloride as a raw material) and other unfavorable factors.

[0012] 4. Preparation of sulfuryl fluoride using sulfur dioxide as a raw material

[0013] Journal of the American Chemical Society, Vol. 78 (1956), pp. 1553-1556 discloses preparation of sulfuryl fluoride using sulfur dioxide and silver fluoride as raw materials. US2772124 and US3320030 disclose synthesis of sulfuryl fluoride using sulfur dioxide, hydrogen fluoride, chlorine as raw materials under catalysis of Pd / C and other catalysts.

[0014] Currently, in the preparation method using sulfur dioxide and chlorine as raw materials, there are problems such as harsh high temperature reaction conditions, high cost and easy deactivation of catalyst, many by-product reactions of product, complex post-treatment process, more waste water, and low yield.

[0015] Therefore, it is necessary to provide a new method for preparing sulfuryl fluoride, which has mild reaction conditions, high product yield and purity, material recycling, less waste, and is suitable for industrial production. SUMMARY

[0016] The purpose of the example embodiments of the present application is to solve the above and other deficiencies in the prior art. The present application uses sulfur dioxide, chlorine and organic base-hydrogen fluoride complex as reaction raw materials, which can react at a relatively mild temperature (for example, room temperature and the like), and the generated sulfuryl fluoride gas is then absorbed by an absorption device containing organic base-hydrogen fluoride complex and optionally a solvent, and then the impurity gas in the sulfuryl fluoride gas is removed by condensation, compression and other steps, so that high purity sulfuryl fluoride product can be obtained.

[0017] The present application provides a method for producing sulfuryl fluoride, the method comprising:

[0018] (1) providing a reaction stream comprising an organic base-hydrogen fluoride complex; and

[0019] (2) introducing sulfur dioxide and chlorine into the reaction stream comprising the organic base-hydrogen fluoride complex to form a product stream comprising sulfuryl fluoride.

[0020] In some embodiments, in the organic base-hydrogen fluoride complex, the organic base comprises pyridine, pyridine derivatives, tertiary amines, and any combination thereof.

[0021] In some embodiments, the organic base is a combination of one or more selected from the group consisting of N,N-dimethylaniline, N,N-diethylaniline, N-methylpiperidine, N-ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylpiperazine, N,N-diethylpiperazine, tri-n-butylamine, tri-n-propylamine, triethylamine, trimethylamine, N,N-diisopropylethylamine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethylpropylenediamine.

[0022] In some embodiments, in the organic base-hydrogen fluoride complex, the molar ratio of nitrogen atom to hydrogen fluoride is 1:(0.8-10).

[0023] In some embodiments, the molar ratio of chlorine gas to sulfur dioxide is 1:(1.0-2.0).

[0024] In some embodiments, the molar ratio of sulfur dioxide to fluorine atom in the organic base-hydrogen fluoride complex is 1:(2.0-20.0).

[0025] In some embodiments, the reaction stream further comprises a solvent.

[0026] In some embodiments, the reaction is carried out at a temperature of -20°C to 60°C.

[0027] In some embodiments, the method further comprises:

[0028] (3) condensing the product stream of step (2) at a temperature of -30°C to -10°C to form a condensate and a gas stream;

[0029] (4) washing the gas stream with an organic base-hydrogen fluoride complex and optionally a washing liquid at a temperature of -20°C to 60°C.

[0030] In some embodiments, the reaction is carried out in a batch tank reactor or a continuous pipeline reactor.

[0031] Compared with the prior art, the method of the present application has the characteristics of mild reaction conditions, high product yield, high purity, etc.; moreover, various raw materials can be recycled and reused, and the amount of waste is reduced.

[0032] Other features and aspects will become apparent from the following detailed description and claims. DETAILED DESCRIPTION

[0033] Unless otherwise defined, technical or scientific terms used in the claims and specification have their ordinary meaning as understood by one of ordinary skill in the art.

[0034] As used herein, the term "about" when used in reference to a numerical value, such as the amount of an ingredient in a composition, a concentration, a process temperature, a process time, a flow rate, and the like, or a dimension of an element of an assembly, and the like, means that modifications of + / - 10% are made to the numerical value, e.g., from routine measurement and process variation in making or using the formulation; from incidental errors during such processes; from differences in the purity or composition of the manufacturing, source, or starting materials used to practice the method; and the like.

[0035] As used herein, when a numerical range, such as 5-25, is given, this means at least 5 or not less than 5 and separately and independently not more than or less than 25. In some embodiments, such a range can be independently defined as not less than 5, and separately and independently not more than 25. Values having such a range, such as 10, -15, or 10-20, also separately and independently include the lower and upper values of the range in the same manner.

[0036] As used herein, unless specifically indicated otherwise, a "wt.%" or "weight percent" of a component is based on the total weight of the composition or article in which the component is contained. The terms "comprise" or "comprising", and similar words, mean that the elements or articles listed after the "comprise" or "comprising" are encompassed by the "comprise" or "comprising", and do not exclude other elements or articles.

[0037] In the prior art process for preparing sulfuryl fluoride from sulfur dioxide, chlorine and hydrogen fluoride, the reaction temperature is at 150℃, and a noble catalyst such as Pd / C is used. The present invention uses a complex of an inexpensive organic base and hydrogen fluoride as both a catalyst and a fluorinating agent, and has the advantages of mild reaction conditions, fast reaction speed, high conversion rate, abundant supply of raw materials, low price, and the like. In the present invention, the reaction process of sulfur dioxide and chlorine with the hydrogen fluoride complex does not require the formation of a sulfuryl chloride intermediate. Obviously, the reaction mechanism of the present invention is completely different from that of CN202210110583.8. Moreover, the prior art process for preparing sulfuryl chloride from sulfur dioxide and chlorine is relatively harsh, such as the need for dry sulfur dioxide and chlorine to react at high temperature in the presence of a catalyst such as activated carbon, camphor, and the like. Therefore, a person skilled in the art would not think or expect that it is possible to directly use sulfur dioxide and chlorine to replace the complex of sulfuryl chloride and hydrogen fluoride to prepare sulfuryl fluoride under the reaction conditions of the similar patent application CN202210110583.8.

[0038] In the present invention, the method for producing sulfuryl fluoride comprises: (1) providing a reaction stream comprising an organic base-hydrogen fluoride complex. The organic base-hydrogen fluoride complex can be prepared from hydrogen fluoride and an organic base, or can be obtained by re-proportioning an organic base-hydrogen fluoride complex product that has been industrially produced or a commercially available organic base-hydrogen fluoride complex according to the needs of the present invention. Moreover, in the present invention, the organic base-hydrogen fluoride complex used in the reaction of the present invention is prepared by re-proportioning the recovered organic base, hydrogen fluoride or a commercially available hydrogen fluoride complex, thereby recycling the organic base and reducing the discharge of waste.

[0039] In the present invention, the organic base includes pyridine, pyridine derivatives, tertiary amines (e.g., substituted anilines or aliphatic amines) and any combination thereof. In a specific embodiment, the organic base is a combination of one or more selected from the group consisting of pyridine, N,N-dimethylaniline, N,N-diethylaniline, N-methylpiperidine, N-ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylpiperazine, N,N-diethylpiperazine, tri-n-butylamine, tri-n-propylamine, triethylamine, trimethylamine, N,N-diisopropylethylamine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethylpropylenediamine.

[0040] In a specific embodiment, the molar ratio of nitrogen atoms to hydrogen fluoride in the organic base-hydrogen fluoride complex is about 1:(0.8-10), 1:(0.9-9), 1:(1.0-8.0), 1:(2.0-7.0), 1:(3.0-6.0) or 1:(4.0-5.0). In a preferred embodiment, the molar ratio of nitrogen atoms to hydrogen fluoride in the organic base-hydrogen fluoride complex is 1:(0.9-3.0).

[0041] In the present invention, the reaction stream comprising the organic base-hydrogen fluoride complex in step (1) can further comprise sulfur dioxide. In a specific embodiment, the reaction stream comprising the organic base-hydrogen fluoride complex and sulfur dioxide is premixed. Since the reaction of the present invention is usually carried out under conditions of excess sulfur dioxide, in the case where sulfur dioxide is premixed in the reaction stream of step (1), the amount of sulfur dioxide added in step (2) can be reduced or even omitted, as long as sulfur dioxide is in excess in the overall reaction.

[0042] In a specific embodiment of the present invention, the method for producing sulfuryl fluoride comprises:

[0043] (1) providing a reaction stream comprising an organic base-hydrogen fluoride complex and a first portion of sulfur dioxide; and

[0044] (2) introducing a second portion of sulfur dioxide and chlorine gas into the reaction stream comprising the organic base-hydrogen fluoride complex, the reaction forming a product stream comprising sulfuryl fluoride; wherein the first portion of sulfur dioxide is in an amount of 0 wt% to 100 wt% of the total weight of sulfur dioxide; and the second portion of sulfur dioxide is in an amount of 0 wt% to 100 wt% of the total weight of sulfur dioxide.

[0045] In the present application, the method for producing sulfuryl fluoride comprises: (2) introducing sulfur dioxide and chlorine gas into the reaction stream comprising the organic base-hydrogen fluoride complex, the reaction forming a product stream comprising sulfuryl fluoride. The order of introducing sulfur dioxide and chlorine gas into the reaction stream is not particularly limited. In some embodiments, sulfur dioxide can be introduced into the reaction stream first, followed by the introduction of chlorine gas. In some embodiments, sulfur dioxide and chlorine gas can be introduced into the reaction stream simultaneously. Moreover, in the present application, the term "introducing" includes adding in a continuous manner (for example, suitable for a continuous pipe reactor), and also includes adding in a batch manner intermittently (for example, suitable for a tank reactor). In embodiments, the molar ratio of chlorine gas to sulfur dioxide is about 1:(1.0-2.0), 1:(1.0-1.8), 1:(1.0-1.5), or 1:(1.0-1.2).

[0046] In the present application, the molar ratio of sulfur dioxide to fluorine atoms in the organic base-hydrogen fluoride complex is about 1:(2.0-20.0), 1:(3.0-18.0), 1:(4.0-16.0), 1:(5.0-14.0), 1:(6.0-12.0), 1:(7.0-10.0), or 1:(8.0-9.0).

[0047] In the present application, the reaction stream comprising the organic base-hydrogen fluoride complex can be a reaction stream comprising only the organic base-hydrogen fluoride complex or a reaction stream consisting of the organic base-hydrogen fluoride complex. In embodiments, the reaction stream can comprise a solvent in addition to the organic base-hydrogen fluoride complex. In embodiments, the solvent is an aprotic solvent selected from esters, amides, nitriles, and the like. In embodiments, the solvent is selected from methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, N,N-dimethylformamide, N,N-diethylacetamide, N-methylpyrrolidone, acetonitrile, propionitrile, or any combination thereof.

[0048] In embodiments, the reaction is carried out at a temperature of -20°C to 60°C, -10°C to 50°C, 0°C to 40°C, 10°C to 30°C, or 15°C to 25°C. In embodiments, the reaction can be carried out at room temperature.

[0049] In specific embodiments, the reaction does not require the use of any catalyst, such as Pd / C catalyst, activated carbon, camphor, etc. In the present application, the reactor used to perform the reaction includes, but is not limited to, a batch tank reactor, a continuous pipeline reactor, etc.

[0050] In specific embodiments, the method further comprises: (3) condensing the product stream of step (2) at a temperature of -30°C to -10°C, -25°C to -15°C, or about -20°C to form a condensate and a gas stream.

[0051] In specific embodiments, the method further comprises: (4) washing the gas stream with a washing solution comprising an organic base-hydrogen fluoride complex and optionally a solvent at a temperature of -20°C to 60°C, -10°C to 50°C, 0°C to 40°C, 10°C to 30°C, 15°C to 25°C, or room temperature. The organic base-hydrogen fluoride complex and solvent can be the same as or different from the organic base-hydrogen fluoride complex and solvent involved in the reaction, if any.

[0052] In specific embodiments, when a solvent is used, the organic base and chlorine element can form hydrochloric acid salt of the organic base in the reaction, which can be precipitated out, facilitating separation from the reaction solution by centrifugation, filtration, etc., and the reaction solution can be recycled for the preparation of sulfuryl fluoride. The hydrochloric acid salt of the organic base can be neutralized by a soluble basic salt (e.g., sodium hydroxide or potassium hydroxide, etc.) to recover the organic base for recycling to prepare the organic base-hydrogen fluoride complex. On the other hand, the chloride (e.g., sodium chloride, potassium chloride, etc.) formed by neutralization of the chlorine element can be electrolyzed to produce chlorine gas and sodium hydroxide or potassium hydroxide; the chlorine gas can be recycled for the preparation of sulfuryl fluoride, and the sodium hydroxide or potassium hydroxide can be used to neutralize the hydrochloric acid salt of the organic base, and the hydrogen gas produced by electrolysis can be used as energy.

[0053] In the prior art, the existing process for product purification includes multiple steps such as alkali washing, water washing, concentrated sulfuric acid drying, etc., which is complex and brings additional problems of post-treatment of the absorption liquid. The present application directly uses one of the reaction raw materials (i.e., the organic base-hydrogen fluoride complex or a suitable solution thereof) as an impurity absorption material. The absorption material can be used as a reaction liquid supplement to the reaction system after use, thereby maintaining the freshness and stability of the impurity absorption material, effectively simplifying the post-treatment process, and reducing the generation of three wastes.

[0054] In the present application, the purity and yield are measured in the following manner.

[0055] 1. Purity

[0056] Detection method: gas chromatography, internal standard method.

[0057] The product of the present application has high purity, and the impurities are known compounds. Therefore, the content of impurities is determined by using an internal standard method, and the purity of the product is determined by using the method of 100% minus the content of impurities.

[0058] Product purity = 100% - impurity content%.

[0059] 2. Yield

[0060] In the embodiments of the present application, sulfur dioxide is in excess, so chlorine is used as the basis for measurement.

[0061] Yield = (mass of sulfuryl fluoride / molecular weight of sulfuryl fluoride) / (mass of chlorine / molecular weight of chlorine) x 100%

[0062] Examples

[0063] Examples A1-A3

[0064] According to Table 1, an organic base-hydrogen fluoride complex and a solvent are added to a batch tank reactor, the reaction temperature is maintained and stirring is carried out; then, sulfur dioxide and chlorine are introduced, and a reaction product containing sulfuryl fluoride is formed. According to Table 1, the reaction product is washed by solution and condensed, and finally sulfuryl fluoride is obtained.

[0065] Table 1:

[0066]

[0067] Table 1: continued

[0068]

[0069]

[0070] Examples B1-B9

[0071] According to Table 2, an organic base-hydrogen fluoride complex and a solvent are introduced into a continuous pipeline reactor, the reaction temperature is maintained and stirring is carried out; then, sulfur dioxide and chlorine are introduced, and a reaction product containing sulfuryl fluoride is formed. During the reaction, the organic base-hydrogen fluoride complex and the solvent are supplemented to match the reactant ratio shown in Table 2.

[0072] The solids generated during the reaction are removed by filtration, and the filtrate after filtration is returned to the continuous pipeline reactor to continue to serve as the reaction solvent. The reaction product is washed by solution and / or condensed, and finally sulfuryl fluoride is obtained.

[0073] Table 2:

[0074]

[0075]

[0076] Table 2: continuation

[0077]

[0078]

[0079] Notes:

[0080] 1. The total amount of reaction is based on about 150 g of chlorine gas;

[0081] 2. The amount of organic solvent is relative to the amount of organic base- hydrogen fluoride complex used;

[0082] 3. The material ratio and yield are calculated based on chlorine gas;

[0083] 4. Example B8 is purified by two steps: a, solution washing; b, low temperature condensation.

[0084] While the application has been described in connection with specific embodiments thereof, it will be understood that it is capable of modification and variation and is limited only by the true spirit and scope of the inventive concepts. Accordingly, it is intended to be broadly within the scope of the claims.

Claims

1. A method for producing sulfuryl fluoride, the method comprising: (1) Provide a reaction stream containing an organic base-hydrogen fluoride complex; and (2) Sulfur dioxide and chlorine are introduced into the reaction stream containing organic base-hydrogen fluoride complex to form a product stream containing sulfuryl fluoride.

2. The method according to claim 1, characterized in that, In the organic base-hydrogen fluoride complex, the organic base includes pyridine, pyridine derivatives, tertiary amines, and any combination thereof.

3. The method according to claim 2, characterized in that, The organic base is selected from one or more combinations of N,N-dimethylaniline, N,N-diethylaniline, N-methylpiperidine, N-ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylpiperazine, N,N-diethylpiperazine, tri-n-butylamine, tri-n-propylamine, triethylamine, trimethylamine, N,N-diisopropylethylamine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N,N,N-tetramethylethylenediamine, and N,N,N,N,N-tetramethylpropanediamine.

4. The method according to claim 1, characterized in that, In the organic base-hydrogen fluoride complex, the molar ratio of nitrogen atoms to hydrogen fluoride is 1:(0.8-10).

5. The method according to claim 1, characterized in that, The molar ratio of chlorine to sulfur dioxide is 1:(1.0-2.0).

6. The method according to claim 1, characterized in that, The molar ratio of fluorine atoms in the sulfur dioxide-organic base-hydrogen fluoride complex is 1:(2.0-20.0).

7. The method according to claim 1, characterized in that, The reaction stream also contains a solvent.

8. The method according to claim 1, characterized in that, The reaction was carried out at temperatures ranging from -20°C to 60°C.

9. The method according to claim 1, characterized in that, The method further includes: (3) The product stream from step (2) is condensed at a temperature of -30°C to -10°C to form a condensate and a gas stream; and (4) The gas stream is washed with an organic base-hydrogen fluoride complex and optionally a washing liquid at a temperature of -20°C to 60°C.

10. The method according to claim 1, characterized in that, The reaction is carried out in a batch reactor or a continuous pipeline reactor.

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