Preparation method and application of bis (trialkylsilyl) disulfonate

Abstract

The invention discloses a preparation method and application of bis (trialkylsilyl) disulfonate, and the preparation method comprises the following steps: (1) soaking a porous carrier material in a mixed salt solution, carrying out heating treatment in an inert atmosphere, cooling, and filtering to obtain a crude product, the mixed salt comprising a magnesium salt and an aluminum salt; (2) adding the crude product into an ammonia water solution for reaction, filtering and drying to obtain a catalyst; (3) reacting a disulfonic acid compound with the dewatered alkyl disiloxane under the action of a catalyst to obtain bis (trialkylsilyl) disulfonate as shown in a formula 1; # imgabs0 # R1-R3 are respectively and independently selected from a C1-C10 alkyl group, a C1-C5 alkyl group substituted by a cyano group or a C1-C5 alkyl group substituted by a C2-C4 alkenyl group, and R4 is selected from a C1-C4 alkyl group. The preparation method provided by the invention is very suitable for large-scale industrial production of bis (trialkylsilyl) disulfonate.

Description

Technical Field

[0001] The invention relates to the technical field of compound synthesis, and in particular to a preparation method and application of bis(trialkylsilyl)disulfonate. Background Art

[0002] With the development of lithium-ion batteries, in order to improve the performance of lithium-ion batteries, the research on electrolyte additives for lithium-ion batteries is also a current research hotspot. Among them, bis(trialkylsilyl)disulfonates are increasingly attracting people's attention due to their small amount and high efficacy. The use of bis(trialkylsilyl)disulfonates is currently one of the more economical and effective methods for improving the performance of lithium-ion batteries. For example, patent document CN116438676 A discloses the use of bis(trialkylsilyl)disulfonates as additives for lithium-ion batteries.

[0003] As for the preparation of bis(trialkylsilyl)disulfonate, the current mainstream method is to react metal salts such as sodium disulfonate, silver disulfonate and barium disulfonate with trialkylchlorosilane, but the cost of metal salts is relatively high, which limits their application in large-scale industrial production. If the metal salt is directly replaced with a disulfonic acid compound, hydrochloric acid (HCl) will be released, which is a highly corrosive gas that not only damages the production equipment, but also increases the difficulty of environmental control and safety hazards in the production process, thereby limiting its application in large-scale industrial production.

[0004] Therefore, there is an urgent need for a preparation method and application of bis(trialkylsilyl)disulfonate to solve the deficiencies of the prior art. Summary of the invention

[0005] In view of the above problems, the object of the present invention is to provide a preparation method and application of bis(trialkylsilyl)disulfonate. The preparation method of the present invention is very suitable for large-scale industrial production of bis(trialkylsilyl)disulfonate.

[0006] To achieve the above objectives, the first aspect of the present invention provides a method for preparing a bis(trialkylsilyl)disulfonate, comprising the following steps:

[0007] (1) immersing a porous carrier material in a mixed salt solution and heating it under an inert atmosphere, cooling it down and filtering it to obtain a crude product, wherein the mixed salt includes a magnesium salt and an aluminum salt;

[0008] (2) adding the crude product to an aqueous ammonia solution for reaction, filtering and drying to obtain a catalyst;

[0009] (3) reacting the disulfonic acid compound and the alkyl disiloxane after water removal under the action of a catalyst to obtain a bis(trialkylsilyl) disulfonate ester as shown in Formula 1;

[0010]

[0011] R1 to R3 are each independently selected from C1 to C10 alkyl groups, C1 to C5 alkyl groups substituted with cyano groups or C1 to C5 alkyl groups substituted with C2 to C4 alkenyl groups, and R4 is selected from C1 to C4 alkyl groups.

[0012] Compared with the prior art, the present invention directly synthesizes the bis(trialkylsilyl)disulfonate shown in Formula 1 by disulfonic acid compounds and alkyldisiloxane under the action of a catalyst. Specifically, compared with the highly corrosive trialkylchlorosilane used in the conventional method, the alkyldisiloxane raw material selected in the present application has low toxicity and low corrosivity, so it is safer and more environmentally friendly; at the same time, the byproduct of the reaction of disulfonic acid compounds and alkyldisiloxane is only water, which avoids the emission of highly corrosive gases and protects the equipment from corrosion; in addition, the present application first heat-treats the porous carrier material in a mixed salt (magnesium salt and aluminum salt), and then reacts chemically in an ammonia environment to generate a catalyst, which is an active solid base catalyst, which can not only effectively catalyze the reaction of disulfonic acid compounds and alkyldisiloxane, but also the catalyst can be recycled and reused, which is conducive to reducing costs. Therefore, the preparation method of the present invention is very suitable for large-scale industrial production of bis(trialkylsilyl)disulfonate, which is conducive to meeting the growing market demand for bis(trialkylsilyl)disulfonate.

[0013] Furthermore, any one of R1 to R3 of the present invention is selected from C1 to C10 alkyl, C1 to C5 alkyl substituted with cyano or C1 to C5 alkyl substituted with C2 to C4 alkenyl, and the other two of R1 to R3 are methyl.

[0014] Furthermore, the porous carrier material of the present invention comprises at least one of 4A molecular sieve, volcanic rock and zeolite.

[0015] Further, the ion concentration of the mixed salt of the present invention is 0.5-1.3 mol / L, and the molar ratio of magnesium salt to aluminum salt is 1:0.8-1.5. The porous carrier material is subjected to heat treatment in the mixed salt (magnesium salt and aluminum salt), and a magnesium-aluminum composite oxide structure with abundant active sites can be formed on the porous carrier. These active sites have high catalytic activity for the reaction of disulfonic acid compounds with alkyl disiloxanes, and can effectively accelerate the reaction process; at the same time, the magnesium-aluminum composite oxide structure is generally more stable than a single metal oxide, especially under high temperature or long-term use conditions, it can maintain good structural integrity and catalytic performance, and extend the service life of the catalyst. Specifically, the ion concentration of the mixed salt may be, but is not limited to, 0.5 mol / L, 0.8 mol / L, 1.0 mol / L, 1.3 mol / L. The molar ratio of magnesium salt to aluminum salt may be, but is not limited to, 1:0.8, 1:1, 1:1.2, 1:1.5.

[0016] Further, the mass ratio of the disulfonic acid compound to the alkyl disiloxane of the present invention is 0.75 to 1.1:1, and the mass ratio of the catalyst to the alkyl disiloxane is 0.029 to 0.15:1. The mass ratio of the disulfonic acid compound to the alkyl disiloxane may be, but is not limited to, 0.75:1, 0.85:1, 0.95:1, and 1.1:1. The mass ratio of the catalyst to the alkyl disiloxane is 0.029:1, 0.05:1, 0.08:1, 0.10:1, and 0.15:1.

[0017] Furthermore, step (3) of the present invention comprises mixing a disulfonic acid compound, an alkyl disiloxane after dehydration treatment, and a catalyst, heating and reacting under reflux until no water is generated, and then filtering and evaporating to obtain a bis(trialkylsilyl) disulfonate as shown in Formula 1. The filtration is to remove the catalyst, and the evaporation is to remove the solvent and residual alkyl disiloxane.

[0018] Furthermore, the heating treatment in step (1) of the present invention includes: keeping warm at 70-85°C for 0.5-3h. Specifically, the temperature of the heating treatment may be, but not limited to, 70°C, 75°C, 80°C, 85°C; and the keeping time may be, but not limited to, 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h.

[0019] Further, step (2) of the present invention comprises adding the crude product to a 0.1-0.5 mol / L ammonia solution, and reacting at 40-65°C for 5-10 hours. Specifically, the concentration of the ammonia solution may be, but not limited to, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L; the reaction temperature may be, but not limited to, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C; the reaction time may be, but not limited to, 5h, 6h, 7h, 8h, 9h, 10h.

[0020] Furthermore, the drying temperature in step (2) of the present invention is 100-120° C. The drying temperature may be, but is not limited to, 100° C., 105° C., 110° C., 115° C., or 120° C.

[0021] Furthermore, the disulfonic acid compound of the present invention includes at least one of 1,2-ethanedisulfonic acid, 1,3-propanedisulfonic acid, and methyldisulfonic acid.

[0022] Further, the alkyl disiloxane of the present invention includes at least one of hexamethyl disiloxane, 1,3-octyltetramethyl disiloxane, diallyltetramethyl disiloxane and 1,3-bis(3-cyanoethyl)tetramethyl disiloxane.

[0023] Furthermore, the water removal treatment of the present invention comprises: adding alkyl disiloxane to an azeotropic organic solvent, heating and reflux until no water is generated.

[0024] Furthermore, the azeotropic organic solvent of the present invention is toluene or xylene.

[0025] Accordingly, the present invention also provides an application of a bis(trialkylsilyl)disulfonate, wherein the bis(trialkylsilyl)disulfonate prepared by the above-mentioned preparation method of the bis(trialkylsilyl)disulfonate is used as an additive for lithium ion batteries. This preparation method is particularly suitable for large-scale production of bis(trialkylsilyl)disulfonate, so it is beneficial to promote the application of bis(trialkylsilyl)disulfonate in lithium ion batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the bis(trialkylsilyl)disulfonate prepared in Example 1 of the present invention.

[0027] Figure 2 This is the carbon NMR spectrum of the bis(trialkylsilyl)disulfonate prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0028] In order to better illustrate the purpose, technical scheme and beneficial effects of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be noted that the following implementation method is a further explanation of the present invention and should not be used as a limitation of the present invention.

[0029] Example 1

[0030] This embodiment provides a method for preparing a bis(trialkylsilyl)disulfonate, comprising the following steps:

[0031] (1) immersing a 4A molecular sieve in a mixed salt solution with an ion concentration of 0.5 mol / L and heating to 70° C. under a nitrogen inert atmosphere, keeping the temperature for 0.5 h, then cooling and filtering to obtain a crude product, wherein the mixed salt is composed of magnesium nitrate and aluminum nitrate in a molar ratio of 1:0.8;

[0032] (2) adding the crude product to a 0.1 mol / L aqueous ammonia solution and reacting it at 40°C for 5 h, filtering it and drying it at 100°C to obtain a catalyst;

[0033] (3) adding 16.2 kg of hexamethyldisiloxane to 120 kg of toluene, heating and reflux until no water is generated, then adding 0.48 kg of catalyst, stirring for 10 min, then adding 17.6 kg of methyl disulfonic acid, heating and reflux until no water is generated, then filtering and evaporating to obtain bis(trialkylsilyl) disulfonate;

[0034] After calculation, the yield was 92.6%. The structure of bis(trialkylsilyl)disulfonate was determined by liquid chromatography-mass spectrometry (LC-MS) as shown below. Meanwhile, the nuclear magnetic resonance hydrogen spectrum and carbon spectrum of bis(trialkylsilyl)disulfonate were as shown below. Figure 1 , Figure 2 As shown, it can also be confirmed that the structure of bis(trialkylsilyl)disulfonate is as shown below.

[0035]

[0036] Example 2

[0037] This embodiment provides a method for preparing a bis(trialkylsilyl)disulfonate, comprising the following steps:

[0038] (1) immersing volcanic rock in a mixed salt solution with an ion concentration of 0.8 mol / L and heating to 75° C. under a nitrogen inert atmosphere, keeping the temperature for 1 hour, then cooling and filtering to obtain a crude product, wherein the mixed salt is composed of magnesium nitrate and aluminum nitrate in a molar ratio of 1:1;

[0039] (2) adding the crude product to a 0.3 mol / L aqueous ammonia solution and reacting it at 45° C. for 8 h, filtering it and drying it at 110° C. to obtain a catalyst;

[0040] (3) adding 19.4 kg of 1,3-octyltetramethyldisiloxane to 120 kg of toluene, heating and reflux until no water is generated, then adding 1.94 kg of catalyst, stirring for 20 min, and then adding 19.0 kg of 1,2-ethanedisulfonic acid, heating and reflux until no water is generated, then filtering and evaporating to obtain bis(trialkylsilyl)disulfonate;

[0041] After calculation, the yield was 90.2%; the structure of bis(trialkylsilyl)disulfonate was determined by liquid chromatography-mass spectrometry (LC-MS) as shown below:

[0042]

[0043] Example 3

[0044] This embodiment provides a method for preparing a bis(trialkylsilyl)disulfonate, comprising the following steps:

[0045] (1) immersing the zeolite in a mixed salt solution with an ion concentration of 0.5 mol / L and heating to 70° C. under a nitrogen inert atmosphere for 2 h, then cooling and filtering to obtain a crude product, wherein the mixed salt is composed of magnesium nitrate and aluminum nitrate in a molar ratio of 1:1.5;

[0046] (2) adding the crude product to a 0.1 mol / L ammonia solution and reacting it at 40°C for 5 h, filtering it and drying it at 120°C to obtain a catalyst;

[0047] (3) adding 24.3 kg of diallyltetramethyldisiloxane to 120 kg of toluene, heating and reflux until no water is generated, then adding 2.5 kg of catalyst, stirring for 30 min, and then adding 20.4 kg of 1,3-propanedisulfonic acid, heating and reflux until no water is generated, then filtering and evaporating to obtain bis(trialkylsilyl)disulfonate;

[0048] After calculation, the yield was 89.9%; the structure of bis(trialkylsilyl)disulfonate was determined by liquid chromatography-mass spectrometry (LC-MS) as shown below:

[0049]

[0050] Example 4

[0051] This embodiment provides a method for preparing a bis(trialkylsilyl)disulfonate, comprising the following steps:

[0052] (1) immersing a 4A molecular sieve in a mixed salt solution with an ion concentration of 1.3 mol / L and heating to 85° C. under a nitrogen inert atmosphere, keeping the temperature for 3 h, then cooling and filtering to obtain a crude product, wherein the mixed salt is composed of magnesium nitrate and aluminum nitrate in a molar ratio of 1:1.1;

[0053] (2) adding the crude product to a 0.1 mol / L ammonia solution and reacting it at 40°C for 10 h, filtering it and drying it at 120°C to obtain a catalyst;

[0054] (3) adding 16.2 kg of 1,3-bis(3-cyanoethyl)tetramethyldisiloxane to 130 kg of toluene, heating and reflux until no water is generated, then adding 0.78 kg of catalyst, stirring for 30 min, then adding 17.6 kg of methyl disulfonic acid, heating and reflux until no water is generated, then filtering and evaporating to obtain bis(trialkylsilyl) disulfonate;

[0055] After calculation, the yield was 91.8%; the structure of bis(trialkylsilyl)disulfonate was determined by liquid chromatography-mass spectrometry (LC-MS) as shown below:

[0056]

[0057] Comparative Example 1

[0058] This comparative example provides a method for preparing a bis(trialkylsilyl)disulfonate, comprising the following steps:

[0059] 16.2 g of hexamethyldisiloxane was added to 120 g of toluene, and the mixture was heated under reflux until no water was generated. Then 17.6 g of methyl disulfonic acid was added, and the mixture was heated under reflux until no water was generated. After the reaction was stopped, the mixture was cooled to allow solid to precipitate.

[0060] Liquid chromatography-mass spectrometry (LC-MS) confirmed that the solid was unreacted methanedisulfonic acid, that is, the reaction of Comparative Example 1 did not occur.

[0061] Comparative Example 2

[0062] This comparative example provides a method for preparing a bis(trialkylsilyl)disulfonate, comprising the following steps:

[0063] (1) immersing 4A molecular sieve in a magnesium nitrate solution with an ion concentration of 0.5 mol / L and heating to 70° C. under a nitrogen inert atmosphere for 0.5 h, then cooling and filtering to obtain a crude product;

[0064] (2) adding the crude product to a 0.1 mol / L aqueous ammonia solution and reacting it at 40°C for 5 h, filtering it and drying it at 100°C to obtain a catalyst;

[0065] (3) 16.2 g of hexamethyldisiloxane was added to 120 g of toluene, and the mixture was heated to reflux until no water was generated. Then, 0.48 g of catalyst was added, and after stirring for 10 min, 17.6 g of methyl disulfonic acid was added. The mixture was heated to reflux and reacted until no water was generated. Then, the mixture was filtered and evaporated to obtain bis(trialkylsilyl) disulfonate;

[0066] After calculation, the yield was 78.7%; the structure of bis(trialkylsilyl)disulfonate was determined by liquid chromatography-mass spectrometry (LC-MS) as shown below:

[0067]

[0068] Comparative Example 3

[0069] This comparative example provides a method for preparing a bis(trialkylsilyl)disulfonate, comprising the following steps:

[0070] (1) immersing 4A molecular sieve in an aluminum nitrate solution with an ion concentration of 0.5 mol / L and heating to 70° C. under a nitrogen inert atmosphere for 0.5 h, then cooling and filtering to obtain a crude product;

[0071] (2) adding the crude product to a 0.1 mol / L aqueous ammonia solution and reacting it at 40°C for 5 h, filtering it and drying it at 100°C to obtain a catalyst;

[0072] (3) 16.2 g of hexamethyldisiloxane was added to 120 g of toluene, and the mixture was heated to reflux until no water was generated. Then, 0.48 g of catalyst was added, and after stirring for 10 min, 17.6 g of methyl disulfonic acid was added. The mixture was heated to reflux and reacted until no water was generated. Then, the mixture was filtered and evaporated to obtain bis(trialkylsilyl) disulfonate;

[0073] After calculation, the yield was 76.3%; the structure of bis(trialkylsilyl)disulfonate was determined by liquid chromatography-mass spectrometry (LC-MS) as shown below:

[0074]

[0075] By comparing Example 1 with Comparative Example 1, it can be seen that the present invention first subjects the porous carrier material to a heat treatment in a mixed salt (magnesium salt and aluminum salt), and then conducts a chemical reaction in an ammonia environment to generate a catalyst, which is an active solid base catalyst, which can effectively catalyze the reaction of disulfonic acid compounds and alkyl disiloxane to improve the yield.

[0076] By comparing Example 1 with Comparative Examples 2 to 3, it can be seen that the present invention heat-treats the porous support material in a mixed salt (magnesium salt and aluminum salt) to form a magnesium-aluminum composite oxide structure with abundant active sites on the porous support, and these active sites have a high catalytic activity for the reaction of disulfonic acid compounds with alkyl disiloxanes, which can greatly improve the catalytic efficiency, accelerate the reaction process, and thus improve the yield of the product. However, heat-treating the porous support material in a single magnesium salt or aluminum salt does not form an oxide structure with abundant active sites on the porous support, thereby affecting the yield.

[0077] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, it is not limited to those listed in the embodiments. Those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A method for preparing a bis(trialkylsilyl)disulfonate, characterized in that: The following steps are involved: (1) immersing a porous carrier material in a mixed salt solution and heating it under an inert atmosphere, cooling it down and filtering it to obtain a crude product, wherein the mixed salt comprises a magnesium salt and an aluminum salt; (2) adding the crude product to an aqueous ammonia solution for reaction, filtering and drying to obtain a catalyst; (3) reacting the disulfonic acid compound and the alkyl disiloxane after water removal under the action of the catalyst to obtain the bis(trialkylsilyl) disulfonate of formula 1; R1 to R3 are each independently selected from C1 to C10 alkyl groups, C1 to C5 alkyl groups substituted with cyano groups or C1 to C5 alkyl groups substituted with C2 to C4 alkenyl groups, and R4 is selected from C1 to C4 alkyl groups.

2. The method for preparing bis(trialkylsilyl)disulfonate according to claim 1, characterized in that: The porous support material includes at least one of 4A molecular sieve, volcanic rock and zeolite.

3. The method for preparing bis(trialkylsilyl)disulfonate according to claim 1, characterized in that: The ion concentration of the mixed salt is 0.5-1.3 mol / L, and the molar ratio of the magnesium salt to the aluminum salt is 1:0.8-1.

5.

4. The method for preparing bis(trialkylsilyl)disulfonate according to claim 1, characterized in that: The mass ratio of the disulfonic acid compound to the alkyl disiloxane is 0.75-1.1:1, and the mass ratio of the catalyst to the alkyl disiloxane is 0.029-0.15:

1.

5. The method for preparing bis(trialkylsilyl)disulfonate according to claim 1, characterized in that: The heating treatment in step (1) comprises: keeping warm at 70-85° C. for 0.5-3 h.

6. The method for preparing bis(trialkylsilyl)disulfonate according to claim 1, characterized in that: Step (2) comprises adding the crude product into a 0.1-0.5 mol / L aqueous ammonia solution and reacting the solution at 40-65° C. for 5-10 hours.

7. The method for preparing bis(trialkylsilyl)disulfonate according to claim 1, characterized in that: The disulfonic acid compound includes at least one of 1,2-ethanedisulfonic acid, 1,3-propanedisulfonic acid and methyldisulfonic acid.

8. The method for preparing bis(trialkylsilyl)disulfonate according to claim 1, characterized in that: The alkyl disiloxane includes at least one of hexamethyl disiloxane, 1,3-octyltetramethyl disiloxane, diallyltetramethyl disiloxane, and 1,3-bis(3-cyanoethyl)tetramethyl disiloxane.

9. The method for preparing bis(trialkylsilyl)disulfonate according to claim 1, characterized in that: The water removal treatment comprises: adding the alkyl disiloxane into an azeotropic organic solvent, heating and reflux until no water is generated.

10. An application of a bis(trialkylsilyl)disulfonate, characterized in that: The bis(trialkylsilyl)disulfonate prepared by the method for preparing the bis(trialkylsilyl)disulfonate according to any one of claims 1 to 9 is used as an additive for lithium ion batteries.

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