Preparation method of phosphonyl alkyl sulfonic acid estersil

Abstract

The invention belongs to the field of organic synthesis, and provides a preparation method of phosphonyl alkyl silicon sulfonate, which comprises the following steps: reacting a compound I with a trialkyl silicon compound to obtain a compound II, namely a target product of phosphonyl alkyl silicon sulfonate, # imgabs0 #, wherein n is an integer from 1 to 6; m1, M2 and M3 are independently selected from H or NH4 < + >; r1, R2 and R3 are independently selected from alkyl with the carbon atom number of 1-6. The preparation method provided by the invention is simple in step, the reaction process is easy to control and realize, industrial production is easy, and the prepared product can be used as an electrolyte additive.

Description

Technical Field

[0001] The present invention belongs to the field of organic synthesis, and particularly relates to a method for preparing a silyl phosphonylalkylsulfonate. Background Art

[0002] The use of functional additives is the most economical and efficient way to improve battery performance. By screening and proportioning a small amount of additives, the performance of the electrolyte can be greatly improved, which is also the core research direction in the field of lithium-ion battery electrolytes in recent years.

[0003] Additives containing elements such as phosphorus, sulfur, and silicon are generally considered to be able to improve battery voltage, low-temperature discharge performance, storage performance, etc. For example, the electrolyte additive disclosed in CN118589045A can reduce the initial impedance of the battery, inhibit the growth of the cycle impedance, and improve the rate performance and cycle life of the battery; the high-voltage electrolyte additive disclosed in CN118522950A can improve the cycle stability and rate performance of lithium batteries; the non-aqueous electrolyte and lithium secondary battery containing a phosphonylsulfonic acid compound disclosed in CN103875117B, through the addition and use of the phosphonylsulfonic acid compound simultaneously realizes the improvement of the low-temperature discharge characteristics and storage characteristics of the battery.

[0004] It can be seen that additives containing silicon, phosphorus, and sulfur elements have important effects in improving the comprehensive performance of batteries. Preparing additives that simultaneously contain silicon, phosphorus, and sulfur elements in the chemical structure will have important practical significance. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for preparing a silyl phosphonylalkylsulfonate, which has the advantages of simple preparation steps, environmental protection in the process, easy control and realization of the reaction process, easy industrial production, high purity of the prepared silyl phosphonylalkylsulfonate product, and can be directly used as an electrolyte additive to improve battery performance.

[0006] In order to achieve the above technical purpose, the technical solution adopted by the present invention is: to provide a method for preparing a silyl phosphonylalkylsulfonate, including the following steps: reacting compound I with a trihydrocarbylsilyl compound to obtain compound II, which is the target product of the silyl phosphonylalkylsulfonate;

[0007]

[0008] wherein, n is an integer from 1 to 6; M1, M2, and M3 are independently selected from H or NH4 + ; R1, R2, and R3 are independently selected from hydrocarbyl groups having 1 to 6 carbon atoms.

[0009] Further, in the structural formula of the compound II, n is an integer from 1 to 3.

[0010] Further, the compound II is selected from at least one of the following structural formulas:

[0011]

[0012]

[0013] Further, the trihydrocarbylsilyl compound is selected from at least one of trihydrocarbylsilazane or trihydrocarbylsiloxane.

[0014] Further, the trihydrocarbylsilyl compound is selected from at least one of hexahydrocarbyldisilazane, hexahydrocarbyldisilylurea, heptahydrocarbyldisilazane, trihydrocarbylhydroxyoxysilane, trihydrocarbylacyloxysilane, trihydrocarbylsilylamine, trihydrocarbylsilylimidazole, trihydrocarbylaminooxysilane, trihydrocarbylalkenyloxysilane, trihydrocarbyloximesilane or N,O-bis(trihydrocarbylsilyl)acetamide.

[0015] Further, the trihydrocarbylsilyl compound is selected from at least one of hexamethyldisilazane, heptamethyldisilazane, tetramethyldivinyldisilazane, trimethylmethoxysilane, trimethylethoxysilane, trimethylsilylimidazole, hexamethyldisilylurea, N,O-bis(trimethylsilyl)acetamide, 1,1,3,3-tetramethyl-1,3-bis(3,3,3-trifluoropropyl)disiloxane or 1,1,3,3-tetramethyl-1,3-bis(2-cyanoethyl)disilazane.

[0016] Further, the molar ratio of the trihydrocarbylsilyl compound to the compound I is 3 - 20:1, the reaction temperature is 10 - 135 °C, and the reaction time is 4 - 40 h.

[0017] Further, the molar ratio of the trihydrocarbylsilyl compound to the compound I is 3.5 - 12:1, the reaction temperature is 30 - 135 °C, and the reaction time is 20 - 40 h.

[0018] Further, the obtained product is purified to obtain a phosphonylhydrocarbylsulfonic acid silyl ester with a purity ≥ 99.0 wt%.

[0019] Further, the purification treatment method is at least one of column chromatography or recrystallization.

[0020] The beneficial effects of the present invention are:

[0021] The preparation method of the phosphonylhydrocarbylsulfonic acid silyl ester provided by the present invention does not require the use of chlorosilane compounds, has an environmentally friendly process, simple steps, an easily controllable and realizable reaction process, is easy to industrialize, and the obtained phosphonylhydrocarbylsulfonic acid silyl ester contains phosphorus, sulfur, and silicon elements in its structural formula at the same time, can improve the high-voltage resistance performance of the battery, reduce the DC internal resistance of the battery, improve the high-temperature cycle and high-temperature storage performance, inhibit the gas swelling after high-temperature storage of the battery, and the product purity ≥ 99%, and can be directly used as an electrolyte additive, having good technical effects. Specific Embodiments

[0022] The technical solution of the present invention will be further explained below in conjunction with specific embodiments. However, the following embodiments are only illustrative examples of the present application and do not limit the content of the present application. Those skilled in the art can make improvements or modifications without creative contributions to the content of the present invention according to the inspiration of this specification, and all fall within the protection scope of the present invention.

[0023] The reaction temperature, unless otherwise specified, generally refers to the internal temperature of the reaction materials.

[0024] The reaction pressure, unless otherwise specified, generally refers to the gauge pressure; the definition of the gauge pressure is the difference between the absolute pressure and the atmospheric pressure.

[0025] The present application will be further described below in conjunction with embodiments. Among them, the exemplary structural formula of Compound II is shown in Table 1.

[0026] Table 1 Exemplary Structural Formulas of Compound II

[0027]

[0028]

[0029]

Example 1

[0030] A preparation method of a phosphonylhydrocarbylsulfonic acid silyl ester (II-1) includes the following steps:

[0031]

[0032] In a 250 mL reaction flask equipped with nitrogen protection, magnetic stirring, a thermometer, a water separator, and a reflux condenser, 13.1 g of Compound I-1 and 170.5 g of hexamethyldisiloxane were added, heated to 99 °C - 103 °C and reacted for another 40 h. 3.4 g of water was separated from the water separator. After the reaction, the temperature was lowered, and the excess hexamethyldisiloxane was recovered by vacuum distillation with a water pump to obtain a crude product, which was purified by column chromatography to obtain 16.7 g of Compound II-1 with a purity of 99.0%.

[0033]

Example 2

[0034] A preparation method of phosphonyl hydrocarbyl sulfonic acid silyl ester (Ⅱ-2) comprises the following steps:

[0035]

[0036] Into a 250 mL reaction flask equipped with nitrogen protection, magnetic stirring, a thermometer, and a reflux condenser, add 19.3 g of compound Ⅰ-2 and 100 mL of acetonitrile. Dropwise add 61.0 g of N,O-bis(trimethylsilyl)acetamide at 35 °C - 45 °C. After dropping, raise the temperature to 60 °C - 65 °C and continue the reaction for 24 h. Filter the reaction solution, and under reduced pressure distill the filtrate to recover the solvent and the unreacted N,O-bis(trimethylsilyl)acetamide. Then use column chromatography for purification to obtain 17.1 g of compound Ⅱ-2 with a purity of 99.2%.

[0037]

Example 3

[0038] A preparation method of phosphonyl hydrocarbyl sulfonic acid silyl ester (Ⅱ-6) comprises the following steps:

[0039]

[0040] Into a 250 mL reaction flask equipped with nitrogen protection, magnetic stirring, a thermometer, a reflux condenser, and tail gas absorption, add 30.1 g of compound Ⅰ-6 and 93.2 g of 1,1,3,3-tetramethyl-1,3-divinyldisilazane. Raise the temperature to 130 °C - 135 °C and react for 40 h. Use a water pump to distill under reduced pressure to recover the excess 1,1,3,3-tetramethyl-1,3-divinyldisilazane, and use a water pump to distill under reduced pressure to recover the solvent to obtain a crude product. Then use column chromatography for purification to obtain 40.2 g of compound Ⅱ-6 with a purity of 99.1%.

[0041] In summary, the preparation method of phosphonyl hydrocarbyl sulfonic acid silyl ester provided by the present invention has simple steps, is environmentally friendly in process, the reaction process is easy to control and implement, is easy for industrial production, and the obtained phosphonyl hydrocarbyl sulfonic acid silyl ester has high product purity and can be directly used as an electrolyte additive.

Claims

1. A method for preparing a phosphonylhydrocarbyl sulfonic acid silyl ester, characterized in that, It includes the following steps: Compound I reacts with a trihydrocarbylsilyl compound to obtain Compound II, which is the target product of phosphonylhydrocarbyl sulfonic acid silyl ester; Wherein, n is an integer from 1 to 6; M1, M2, and M3 are independently selected from H or NH4 + ; R1, R2, and R3 are independently selected from hydrocarbon groups having 1 to 6 carbon atoms.

2. The preparation method of the phosphonylhydrocarbyl sulfonic acid silyl ester according to claim 1, characterized in that, In the structural formula of the said Compound II, n is an integer from 1 to 3.

3. The preparation method of the phosphonyl hydrocarbyl sulfonic acid silyl ester according to claim 1, characterized in that, The said Compound II is selected from at least one of the following structural formulas:

4. The preparation method of the phosphonylhydrocarbyl sulfonic acid silyl ester according to claim 1, characterized in that, The said trihydrocarbylsilyl compound is selected from at least one of trihydrocarbylsilazane or trihydrocarbylsiloxane.

5. The method for preparing the phosphonylhydrocarbyl sulfonic acid silyl ester according to claim 4, characterized in that, The said trihydrocarbylsilyl compound is selected from at least one of hexahydrocarbyldisilazane, hexahydrocarbyldisilylurea, heptahydrocarbyldisilazane, trihydrocarbylhydroxyoxysilane, trihydrocarbylacyloxysilane, trihydrocarbylsilylamine, trihydrocarbylsilylimidazole, trihydrocarbylaminooxysilane, trihydrocarbylalkenyloxysilane, trihydrocarbyloximesilane or N,O-bis(trihydrocarbylsilyl)acetamide.

6. The preparation method of the phosphonylhydrocarbyl sulfonic acid silyl ester according to claim 5, characterized in that, The said trihydrocarbylsilyl compound is selected from at least one of hexamethyldisilazane, heptamethyldisilazane, tetramethyldivinyldisilazane, trimethylmethoxysilane, trimethylethoxysilane, trimethylsilylimidazole, hexamethyldisilylurea, N,O-bis(trimethylsilyl)acetamide, 1,1,3,3-tetramethyl-1,3-bis(3,3,3-trifluoropropyl)disiloxane or 1,1,3,3-tetramethyl-1,3-bis(2-cyanoethyl)disilazane.

7. The preparation method of the phosphonylhydrocarbyl sulfonic acid silyl ester according to claim 1, characterized in that, The molar ratio of the said trihydrocarbylsilyl compound to Compound I is 3 to 20:1, the reaction temperature is 10 to 135 °C, and the reaction time is 4 to 40 h.

8. The preparation method of the phosphonylhydrocarbyl sulfonic acid silyl ester according to claim 7, characterized in that, The molar ratio of the said trihydrocarbylsilyl compound to Compound I is 3.5 to 12:1, the reaction temperature is 30 to 135 °C, and the reaction time is 20 to 40 h.

9. The preparation method of the phosphonylhydrocarbyl sulfonic acid silyl ester according to claim 1, characterized in that, The prepared product is purified to obtain a phosphonylhydrocarbyl sulfonic acid silyl ester with a purity ≥ 99.0 wt%.

10. The preparation method of the phosphonylhydrocarbyl sulfonic acid silyl ester according to claim 9, characterized in that, The said purification method is at least one of column chromatography or recrystallization.

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