A method for synthesizing methanesulfonyl methylene disulfonate

Abstract

The present invention discloses a method for synthesizing methylene methane disulfonate, which is characterized in that the method comprises: reacting methylene disulfonyl chloride, hexyldisiloxane and dihalomethane in the presence of a catalyst to generate methylene methane disulfonate, and the catalyst is a composite catalyst composed of an organic amine and polyethylene glycol; wherein, the water content of each raw material is controlled to be less than 20 ppm; this method not only has a high yield and good purity, but also has a safe and controllable reaction process, low cost, and simple operation process. It does not directly use paraformaldehyde and phosphorus pentoxide dehydrating agents, will not cause formaldehyde wastewater and waste gas and phosphorus-containing wastewater, and is safe, environmentally friendly and green in production, and is suitable for industrial application.

Description

[0001] This invention is a divisional application of a Chinese invention patent application with the application date of February 11, 2022, application number 2022101268820, and title "A Preparation Method of Methylene Methanedisulfonate". Technical Field

[0002] This invention belongs to the field of organic synthesis, in particular to a battery electrolyte additive or a pharmaceutical intermediate, and specifically relates to a method for synthesizing methylene methanedisulfonate. Background Art

[0003] Methylene methanedisulfonate (MMDS) can be used as a pharmaceutical preparation for treating leukemia and the like in animals. In terms of lithium batteries, the battery added with MMDS has good high-temperature cycling performance. It is applicable to power batteries, especially power batteries with lithium manganate as the cathode material. MMDS can prevent the Mn melted out at high temperature from adsorbing on the surface of the negative electrode, inhibit the increase in impedance, effectively improve the cycle period characteristics, and can greatly increase its cycle life.

[0004] Patent WO85 / 03075() uses a two-step method to prepare methylene methanedisulfonate: alkyl disulfonyl chloride reacts with silver carbonate to obtain silver alkyl disulfonate; silver alkyl disulfonate reacts with methylene iodide to obtain methylene methanedisulfonate. This method uses silver salts and has a low yield, greatly increasing the production cost and not being suitable for large-scale production;

[0005]

[0006] Patent JP5247436 B2 (Sumitomo Chemical Co., Ltd., Japan) dehydrates and cyclizes methanedisulfonic acid and paraformaldehyde or anhydrous formaldehyde or trioxane with phosphorus pentoxide as a dehydrating agent, dissolves, filters, concentrates, crystallizes, and vacuum-dries with dichloromethane to obtain methylene methanedisulfonate, with a yield of 50%;

[0007] Patent CN10246469 (Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences) uses a mixture of methanedisulfonic acid, phosphorus pentoxide, and a formaldehyde compound, and performs ball-milling reaction for 10 - 50 min to obtain methylene methanedisulfonate;

[0008] The above reactions need to use formaldehyde and use phosphorus pentoxide as a dehydrating agent, and there are certain risks in the scale-up of this process;

[0009]

[0010] Patent CN106916138 (Shandong Yonghao New Materials) uses solvent dehydration, and reacts methanedisulfonic acid with paraformaldehyde at 90 - 180 °C to obtain methylene methanedisulfonate. This process also uses formaldehyde-based substances and carcinogenic benzene-containing substances as solvents for reflux reaction, and the waste water and waste gas containing formaldehyde and the like are not environmentally friendly;

[0011]

[0012] Patent WO2021 / 161943 (Sumitomo Seika Chemicals Co., Ltd., Japan) uses a sulfoxide dehydrating agent. In the presence of sulfur trioxide, methanedisulfonic acid is prepared by reacting methanedisulfonic acid with paraformaldehyde. Since sulfur trioxide is used, sulfuric acid will be produced. At the same time, the sulfoxide reacts with water to produce sulfur dioxide and hydrogen chloride waste gas, resulting in a large reaction acid value, high equipment requirements, high danger, and difficult subsequent purification and acid removal. Summary of the Invention

[0013] The object of the present invention is to overcome one or more deficiencies of the prior art and provide a new method for synthesizing methylene methanedisulfonate. This method not only has a high yield and good purity, but also has a safe and controllable reaction process, low cost, simple operation process, does not directly use paraformaldehyde and phosphorus pentoxide dehydrating agent, will not cause formaldehyde wastewater and waste gas and phosphorus-containing wastewater, and is suitable for industrial application with safe, environmental and green production.

[0014] To achieve the above object, the technical solution adopted by the present invention is:

[0015] A method for preparing methylene methanedisulfonate, the preparation method comprising: mixing and reacting methylene disulfonyl chloride, hexalkyl disiloxane and dihalomethane to form the methylene methanedisulfonate.

[0016] According to some preferred aspects of the present invention, the reaction is carried out in the presence of a catalyst, and the catalyst is a composite catalyst composed of an organic amine and polyethylene glycol.

[0017] According to some preferred aspects of the present invention, the organic amine is triethylamine and / or pyridine.

[0018] According to some preferred aspects of the present invention, the feeding mass ratio of the organic amine to the polyethylene glycol is 1:1 - 10.

[0019] According to some preferred aspects of the present invention, the usage amount of the composite catalyst is 0.1% - 1.0% of the feeding amount of the methylene disulfonyl chloride.

[0020] According to some preferred aspects of the present invention, the feeding molar ratio of the methylene disulfonyl chloride, the hexalkyl disiloxane and the dihalomethane is 1:1 - 1.05:5 - 10.

[0021] According to some preferred aspects of the present invention, the reaction is carried out under reflux conditions and / or under the protection of an inert gas.

[0022] According to some preferred and specific aspects of the present invention, the dihalomethane is dichloromethane and / or dibromomethane; in some preferred embodiments of the present invention, the reaction is refluxed at 50-100°C.

[0023] According to some preferred and specific aspects of the present invention, the hexyldisiloxane is hexamethyldisiloxane and / or hexyldiethyldisiloxane.

[0024] In some preferred embodiments of the present invention, during the preparation process, under the protection of an inert gas, methylene disulfonyl chloride, dihalomethane and a catalyst are added to a reaction vessel, and hexyldisiloxane is added dropwise at 15-30°C. After the addition is complete, the temperature is raised and the reaction is carried out under reflux conditions to produce the methyl methanedisulfonate.

[0025] According to some preferred and specific aspects of the present invention, the reaction time of the reaction is controlled to be 5-20 h. Further, it can be 6-16 h.

[0026] In some embodiments of the present invention, the inert gas is nitrogen or argon.

[0027] In some embodiments of the present invention, the preparation method further includes a post-treatment step after the reaction, and the post-treatment step includes concentration and crystallization carried out in sequence.

[0028] In the present invention, the reaction process can be shown as follows:

[0029]

[0030] wherein, X = Cl or Br, R = CH3 or C2H5.

[0031] Due to the application of the above technical solutions, the present invention has the following advantages compared with the prior art:

[0032] In the present invention, hexyldisiloxane is innovatively used as an oxygen donor, and the produced halosilane can be recycled and can further react directly with water to generate hexamethyldisiloxane, which can participate in the reaction cycle after drying treatment, greatly saving the production cost; at the same time, the dihalomethane in the present invention is both a reactant participating in the reaction and can also function as a solvent, greatly reducing the amount of material added and the number of processes during the reaction process, being beneficial to industrial application, and the reaction is more complete with fewer by-products. In particular, the method for preparing methyl methanedisulfonate in the present invention avoids the problems of formaldehyde wastewater, waste gas and phosphorus-containing wastewater caused by the existing use of paraformaldehyde and phosphorus pentoxide dehydrating agents, reduces the problems and processes of wastewater treatment, is more environmentally friendly and safe, has low requirements for equipment, and can reduce the production cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1For the refined methylene methanedisulfonate prepared in Example 1 1 H-NMR spectrum;

[0034] Figure 2 For the refined methylene methanedisulfonate prepared in Example 1 13 C-NMR spectrum. Detailed implementation manners

[0035] Based on the problems of formaldehyde wastewater, waste gas and phosphorus-containing wastewater caused by using paraformaldehyde and phosphorus pentoxide dehydrating agents in the preparation of methylene methanedisulfonate in the prior art, the present invention provides a method for synthesizing methylene methanedisulfonate, which includes: reacting methylene disulfonyl chloride, hexaalkyl disiloxane and dihalomethane in the presence of a catalyst to generate methylene methanedisulfonate, and the catalyst is a composite catalyst composed of organic amine and polyethylene glycol; wherein, the water content of each raw material is controlled to be less than 20 ppm.

[0036] In some embodiments, the organic amine is triethylamine and / or pyridine; and / or, the dihalomethane is dichloromethane and / or dibromomethane, and the hexaalkyl disiloxane is hexamethyldisiloxane and / or hexaethyldisiloxane; and / or, the molar ratio of the methylene disulfonyl chloride, the hexaalkyl disiloxane and the dihalomethane is 1∶1 - 1.05∶5 - 10.

[0037] In some embodiments, the mass ratio of the organic amine to the polyethylene glycol is 1∶1 - 10; and / or, the usage amount of the composite catalyst is 0.1% - 1.0% of the feeding amount of the methylene disulfonyl chloride, preferably 0.5% - 1.0%, more preferably 0.5% - 0.65%.

[0038] In some embodiments, the reaction is carried out under the protection of an inert gas. Further, as an option, the inert gas is nitrogen or argon.

[0039] In some embodiments, the reaction is refluxed at 50 - 100 °C; and / or, the reaction time of the reaction is controlled to be 5 - 20 h, preferably 6 - 16 h.

[0040] In some embodiments, during the synthesis process, under the protection of an inert gas, methylene disulfonyl chloride, dihalomethane and the catalyst are added into the reaction vessel, and hexaalkyl disiloxane is added dropwise at 15 - 30 °C, and after the dropwise addition is completed within 1 - 2 h, the temperature is raised, and the reaction is carried out under reflux conditions to generate the methylene methanedisulfonate.

[0041] In some embodiments, the method further includes a post-treatment step after the reaction ends, and the post-treatment step includes distillation and concentration, crystallization, pulping, filtration, and vacuum drying in sequence. Further, the temperature of the vacuum drying is 160-180 °C, the solvent used for crystallization is dichloromethane, and the solvent used for pulping is dimethyl carbonate.

[0042] The above solution will be further described below in conjunction with specific embodiments; it should be understood that these embodiments are used to illustrate the basic principles, main features, and advantages of the present invention, and the present invention is not limited by the scope of the following embodiments; the implementation conditions used in the embodiments can be further adjusted according to specific requirements, and the implementation conditions not specified are usually the conditions in conventional experiments.

[0043] Unless otherwise specified in the following embodiments, all raw materials are obtained from commercial purchases or prepared by conventional methods in the art, and the moisture content of each raw material is controlled to be less than 20 ppm.

[0044] Example 1

[0045] Under nitrogen protection, 200 g (96%, 0.9 mol) of methylene disulfonyl chloride, 780 g of dichloromethane, 0.3 g of pyridine, and 0.7 g of polyethylene glycol were added to a 1000 ml four-necked flask (equipped with a spherical condenser). Hexamethyldisiloxane 296.5 g (1.83 mol) was slowly added dropwise at room temperature, and the addition was completed within 1 hour. The temperature was raised to 50 °C and refluxed for 10 h. Distillation and concentration gave 180 g of a wet product of methyl methane disulfonate.

[0046] The above wet product of methyl methane disulfonate was added to a 200 L crystallization kettle, and 300 ml of dichloromethane was added for dissolution. The insoluble matter was filtered out, the filtrate was concentrated, and methyl methane disulfonate was precipitated again. It was pulped with 100 ml of dimethyl carbonate, filtered, and the filter cake was vacuum dried for 24 h (160-180 °C, 5 mmHg) to obtain 142 g of refined methyl methane disulfonate with a purity of 98.5% and a moisture content of 10 ppm. Its 1 1H-NMR spectrum, 13 13C-NMR spectrum are respectively shown in Figure 1 and Figure 2 .

[0047] Example 2

[0048] Under nitrogen protection, 200 g (96%, 0.9 mol) of methylene disulfonyl chloride, 900 g of dibromomethane, 0.4 g of triethylamine, and 0.8 g of polyethylene glycol were added to a 1000 ml four-necked flask (equipped with a spherical condenser). Hexaethyldisiloxane 451 g (1.83 mol) was slowly added dropwise at room temperature, and the addition was completed within 1 hour. The temperature was raised to 100 °C and refluxed for 10 h. Distillation and concentration gave 185 g of a wet product of methyl methane disulfonate.

[0049] The above-mentioned wet methylene bis(methanesulfonate) was added to a 200 L crystallization kettle, and 300 ml of dichloromethane was added for dissolution. The insoluble matter was filtered out. The filtrate was concentrated, and methylene bis(methanesulfonate) was precipitated. It was slurried again with 100 ml of dimethyl carbonate, filtered, and the filter cake was vacuum dried for 24 h (160 - 180 °C, 5 mmHg) to obtain 154 g of refined methylene bis(methanesulfonate) with a purity of 99.5% and a moisture content of 8 ppm.

[0050] Example 3

[0051] Under nitrogen protection, 200 g (96%, 0.9 mol) of methylene disulfonyl chloride, 900 g of dibromomethane, 0.4 g of pyridine, and 0.8 g of polyethylene glycol were added to a 1000 ml four-necked flask (equipped with a spherical condenser). 451 g (1.83 mol) of hexaethyldisiloxane was slowly added dropwise at room temperature, and the addition was completed within 1 hour. The temperature was raised to 100 °C and refluxed for 10 h. After distillation and concentration, 181 g of wet methylene bis(methanesulfonate) was obtained.

[0052] The above-mentioned wet methylene bis(methanesulfonate) was added to a 200 L crystallization kettle, and 300 ml of dichloromethane was added for dissolution. The insoluble matter was filtered out. The filtrate was concentrated, and methylene bis(methanesulfonate) was precipitated. It was slurried again with 100 ml of dimethyl carbonate, filtered, and the filter cake was vacuum dried for 24 h (160 - 180 °C, 5 mmHg) to obtain 152 g of refined methylene bis(methanesulfonate) with a purity of 99.65% and a moisture content of 7 ppm.

[0053] Example 4

[0054] Under nitrogen protection, 2 kg (96%, 9 mol) of methylene disulfonyl chloride, 7800 g of dichloromethane, 4 g of triethylamine, and 9 g of polyethylene glycol were added to a 5 L four-necked flask (equipped with a spherical condenser). 3 kg (18.5 mol) of hexamethyldisiloxane was slowly added dropwise at room temperature, and the addition was completed within 2 hours. The temperature was raised to 50 °C and refluxed for 10 h. After distillation and concentration, 1.83 kg of wet methylene bis(methanesulfonate) was obtained.

[0055] The above-mentioned wet methylene bis(methanesulfonate) was added to a 5 L crystallization kettle, and 2 L of dichloromethane was added for dissolution. The insoluble matter was filtered out. The filtrate was concentrated, and methylene bis(methanesulfonate) was precipitated. It was slurried again with 600 ml of dimethyl carbonate, filtered, and the filter cake was vacuum dried for 24 h (160 - 180 °C, 5 mmHg) to obtain 1.38 kg of refined methylene bis(methanesulfonate) with a purity of 99.96% and a moisture content of 12 ppm.

[0056] The above embodiments are only used to illustrate the technical concept and features of the present invention, and the purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. However, the protection scope of the present invention cannot be limited thereby. Any equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

[0057] In the ranges disclosed herein, endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and a single point value, and between single point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

Claims

1. A method for synthesizing methylene methanedisulfonate, characterized in that, The method includes: reacting methylene disulfonyl chloride, hexaalkyl disiloxane and dihalomethane in the presence of a catalyst to produce methyl methanedisulfonate, wherein the catalyst is a composite catalyst composed of an organic amine and polyethylene glycol; wherein, the water content of each raw material is controlled to be less than 20 ppm.

2. The method for synthesizing methylene methanedisulfonate according to claim 1, wherein The organic amine is triethylamine and / or pyridine; and / or, the dihalomethane is dichloromethane and / or dibromomethane, and the hexaalkyl disiloxane is hexamethyldisiloxane and / or hexaethyldisiloxane; and / or, the feeding molar ratio of methylene disulfonyl chloride, hexaalkyl disiloxane and dihalomethane is 1∶1 - 1.05∶5 - 10.

3. The method for synthesizing methylene methanedisulfonate according to claim 1, wherein The feeding mass ratio of the organic amine to the polyethylene glycol is 1∶1 - 10; and / or, the usage amount of the composite catalyst is 0.1% - 1.0% of the feeding amount of methylene disulfonyl chloride.

4. The method for synthesizing methylene methanedisulfonate according to claim 1, wherein The usage amount of the composite catalyst is 0.5% - 1.0% of the feeding amount of methylene disulfonyl chloride.

5. The method for synthesizing methylene methanedisulfonate according to claim 4, characterized in that, The usage amount of the composite catalyst is 0.5% - 0.65% of the feeding amount of methylene disulfonyl chloride.

6. The method for synthesizing methylene methanedisulfonate according to claim 1, wherein The reaction is carried out under the protection of an inert gas.

7. The method for synthesizing methylene methanedisulfonate according to claim 6, wherein The inert gas is nitrogen or argon.

8. The method for synthesizing methylene methanedisulfonate according to claim 1, wherein, The reaction is refluxed at 50 - 100 °C; and / or, the reaction time of the reaction is controlled to be 5 - 20 h.

9. The method for synthesizing methylene methanedisulfonate according to claim 1, wherein The reaction time of the reaction is controlled to be 6 - 16 h.

10. The method for synthesizing methylene methanedisulfonate according to claim 1, wherein, During the synthesis process, under the protection of an inert gas, methylene disulfonyl chloride, dihalomethane and the catalyst are added into the reaction vessel, and hexaalkyl disiloxane is added dropwise at 15 - 30 °C. After the dropwise addition is completed within 1 - 2 h, the temperature is raised, and the reaction is carried out under reflux conditions to produce the methyl methanedisulfonate.

11. The method for synthesizing methylene methanedisulfonate according to claim 1, wherein The method further includes a post-treatment step after the reaction, and the post-treatment step includes distillation and concentration, crystallization, pulping, filtration, and vacuum drying carried out in sequence.

12. The method for synthesizing methylene methanedisulfonate according to claim 11, wherein, The temperature of the vacuum drying is 160 - 180 °C.

13. The method for synthesizing methylene methanedisulfonate according to claim 11, wherein, The solvent used for crystallization is dichloromethane, and the solvent used for pulping is dimethyl carbonate.

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