A method for preparing lithium allyloxybenzenesulfonate
By treating sodium p-allyloxybenzenesulfonate with a strongly acidic cation exchange resin and lithium salt, the synthesis problem of lithium allyloxybenzenesulfonate was solved, providing a simple and efficient preparation method that improves the performance of lithium-ion batteries.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JIANGSU GUOTAI SUPER POWER NEW MATERIALS
- Filing Date
- 2024-12-23
- Publication Date
- 2026-06-23
AI Technical Summary
The lack of existing technologies for synthesizing lithium allyloxybenzenesulfonate makes it impossible to meet the requirements for electrolyte additives in lithium-ion batteries, thus affecting the capacity retention and cycle life of lithium-ion batteries.
Lithium p-allylbenzenesulfonate was prepared by treating sodium p-allylbenzenesulfonate with a strong acidic cation exchange resin and lithium salt under specific conditions, through ion exchange and reaction, including resin activation, dissolution, reaction and purification steps.
It achieves a simple and efficient preparation process with few side reactions and high product purity, making it suitable as an additive for lithium battery electrolytes to improve battery performance.
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Figure CN122255035A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of compound preparation technology, and specifically to a method for preparing lithium p-allyloxybenzenesulfonate. Background Technology
[0002] Lithium 4-(allyloxy)benzenesulfonate, CAS: 46331-32-2, abbreviated as SAPE-Li, is a white powder at room temperature. Its structural formula is as follows:
[0003]
[0004] Lithium p-allyloxybenzenesulfonate (SAPE-Li) is an important organic lithium salt that can be used as an additive in lithium-ion battery electrolytes. Research on the electrochemical performance of SAPE-Li is still in its early stages both domestically and internationally. Literature studies indicate that adding SAPE-Li to lithium-ion battery electrolytes, causing in-situ polymerization to form p-sulfonic acid-based polyallylphenyl ether (SPAPE-Li), creates a coating on the electrode material surface. This can inhibit electrolyte decomposition and improve the capacity retention and cycle life of lithium-ion batteries. For example, MLDi Vona et al. (Journal of PowerSources. 353 (2017) 95-103) showed that the lithium-ion conductive polymer (SPAPE-Li) directly participates in the formation of the SEI film, exhibiting high area capacity retention and excellent cycle performance at high rates. T. Djenizian et al. (Applied Physics Letters. 7, (2019) 031506) showed that when SPAPE-Li polymer-coated carbon nanotubes are used as the negative electrode material for flexible lithium-ion micro batteries, the capacity of carbon nanotubes can be significantly improved. This is due to the increase in the surface area between carbon nanotubes and polymer electrolyte and the improvement in the quality of the electrode / electrolyte interface.
[0005] However, to date, there have been no detailed reports from academia or industry regarding the synthesis methods of lithium p-allyloxybenzenesulfonate. Therefore, developing an efficient and simple process for preparing lithium p-allyloxybenzenesulfonate is particularly urgent to meet the needs of lithium-ion battery technology development. Summary of the Invention
[0006] The purpose of this invention is to provide a simple method for preparing lithium p-allyloxybenzenesulfonate.
[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0008] This invention provides a method for preparing lithium p-allyloxybenzenesulfonate, wherein sodium p-allyloxybenzenesulfonate is reacted with a strongly acidic cation exchange resin and a lithium salt to obtain the lithium p-allyloxybenzenesulfonate.
[0009] According to some specific embodiments, the lithium salt is one or more of lithium hydroxide, lithium carbonate, lithium oxalate, and lithium chloride.
[0010] According to one specific embodiment, the preparation method includes the following steps:
[0011] (1) Dissolve the sodium p-allyloxybenzenesulfonate in deionized water and pass it through the strong acid cation exchange resin 1 to 3 times to obtain p-allyloxybenzenesulfonic acid.
[0012] (2) Dissolve the p-allyloxybenzenesulfonic acid in alcohol or deionized water, add the lithium salt and react to obtain the lithium p-allyloxybenzenesulfonate.
[0013] Furthermore, the strongly acidic cation exchange resin is activated before each use by soaking in hydrochloric acid and washing with deionized water until neutral.
[0014] Further, in step (2), the alcohol is methanol, ethanol, or a mixture of both.
[0015] Further, in step (2), the concentration of p-allyloxybenzenesulfonic acid dissolved in the alcohol or water is 0.4 to 0.6 mol / L, for example, 0.4 mol / L, 0.5 mol / L or 0.6 mol / L.
[0016] Further, in step (2), the molar ratio of p-allyloxybenzenesulfonic acid to lithium ions in the lithium salt is 1:1.05 to 1.2, for example, 1:1.05, 1:1.1, 1:1.15, 1:1.2.
[0017] Furthermore, in step (2), the reaction is carried out at room temperature.
[0018] Further, in step (2), after the reaction is completed, the product is purified by recrystallization or selective dissolution to obtain the lithium p-allyloxybenzenesulfonate; the solvent used for recrystallization is one or more of methanol, ethanol, and deionized water; the solvent used for selective dissolution is one or more of methanol, ethanol, isopropanol, n-butanol, tetrahydrofuran, and ethylene glycol dimethyl ether.
[0019] Furthermore, the solvent used for recrystallization is ethanol, and the solvent used for selective dissolution is isopropanol.
[0020] Further, in step (2), after the reaction is completed, pure lithium p-allyloxybenzenesulfonate (SAPE-Li) is obtained by filtration, filtrate concentration, recrystallization or selective dissolution, and drying.
[0021] According to another specific embodiment, the preparation method includes the following steps:
[0022] (a) The strongly acidic cation exchange resin was soaked in a saturated sodium chloride aqueous solution, washed with deionized water, soaked in the lithium salt aqueous solution, and washed with deionized water until no lithium salt residue remained in the effluent.
[0023] (b) The sodium p-allyloxybenzenesulfonate is dissolved in water and passed through a strongly acidic cation exchange resin treated in step (a) 1 to 3 times to obtain the lithium p-allyloxybenzenesulfonate; wherein the strongly acidic cation exchange resin is treated in step (a) before each use.
[0024] Further, the concentration of the sodium p-allyloxybenzenesulfonate dissolved in deionized water is 0.1–0.4 mol / L, for example 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.25 mol / L, 0.3 mol / L, 0.35 mol / L or 0.4 mol / L.
[0025] Further, in step (b), after the reaction is completed, the product is purified by recrystallization or selective dissolution to obtain the lithium p-allyloxybenzenesulfonate; the solvent used for recrystallization is one or more of methanol, ethanol, and deionized water; the solvent used for selective dissolution is one or more of methanol, ethanol, isopropanol, n-butanol, tetrahydrofuran, and ethylene glycol dimethyl ether.
[0026] Furthermore, the solvent used for recrystallization is ethanol, and the solvent used for selective dissolution is isopropanol.
[0027] Furthermore, in step (b), after the reaction is complete, the effluent is dried, recrystallized, or selectively dissolved and dried to obtain pure lithium p-allyloxybenzenesulfonate (SAPE-Li).
[0028] According to some specific embodiments, the sodium p-allyloxybenzenesulfonate is prepared by reacting sodium 4-hydroxybenzenesulfonate with allyl bromide under reflux in the presence of sodium methoxide and solvent.
[0029] Furthermore, the molar ratio of the sodium 4-hydroxybenzenesulfonate, the sodium methoxide, and the allyl bromide is 1:1 to 2:1 to 3.
[0030] Further, the reflux temperature is 60–80°C, and the reflux time is 4–12 hours. Even further, the reflux temperature is 70–80°C, and still further, the reflux temperature is 75–80°C.
[0031] Furthermore, the solvent is one or more of methanol, ethanol, tetrahydrofuran, acetone, and dimethyl sulfoxide.
[0032] Furthermore, the specific steps for preparing the sodium p-allyloxybenzenesulfonate are as follows:
[0033] Under nitrogen protection, sodium 4-hydroxybenzenesulfonate was dissolved in methanol, and sodium methoxide methanol solution and allyl bromide were added dropwise. The mixture was refluxed at 60-80°C for 4-12 hours. After the reaction solution was cooled, it was filtered, the solid was washed with a small amount of methanol, and dried to obtain crude sodium p-sulfonate allyl phenyl ether (SAPE-Na).
[0034] Furthermore, under stirring conditions, the sodium methoxide methanol solution is first added dropwise. After the addition is complete, the mixture is stirred at room temperature for 20–40 minutes, and then the allyl bromide is added dropwise.
[0035] Furthermore, the crude sodium allyl oxybenzenesulfonate (SAPE-Na) was purified by recrystallization with deionized water.
[0036] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:
[0037] The preparation method of this invention uses simple and readily available raw materials, has a short preparation time, few side reactions, simple post-processing, and high yield and product purity. The lithium p-allyloxybenzenesulfonate (SAPE-Li) prepared by this invention can be used in the field of lithium battery electrolyte additives. Attached Figure Description
[0038] Figure 1 The image shows the 1H NMR spectrum of lithium allyloxybenzenesulfonate (SAPE-Li). Detailed Implementation
[0039] The reaction equation for the preparation of lithium p-allylbenzenesulfonate according to this invention is as follows:
[0040]
[0041] The 1H NMR spectrum of lithium p-allyloxybenzenesulfonate prepared in this invention is as follows: Figure 1 And as shown below:
[0042] 1H NMR (400MHz, DMSO-d6) δ7.54 (d, 2H, J = 8.66Hz), 6.88 (d, 2H, J = 8.68Hz), 6.0-5. 98(ddt,2H,J=15.75,10.42,5.16Hz),5.4-5.24(m,2H),4.57(d,2H,J=5.12Hz).
[0043] The preparation method of the present invention has the advantages of simple and readily available raw materials, short preparation time, few side reactions, simple post-processing, high yield and high product purity.
[0044] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific applications, and the implementation conditions not specified are conventional conditions in the industry. The technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.
[0045] Unless otherwise specified, the reagents, instruments, etc. used in the following examples are all commercially available products commonly used in the art, or can be prepared using conventional methods in the art. In this invention, unless otherwise specified, all contents are mass contents, "%" is a mass percentage, and parts are parts by mass.
[0046] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the ranges, the endpoint values of the ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. The terms "optional" and "discretionary" mean that they may or may not be included (or may or may not be present).
[0047] Example 1
[0048] Step 1: Purge a 2L four-necked flask with nitrogen for 15 minutes to remove air from the reaction system, replacing the atmosphere with nitrogen. Add 58.2g (0.3mol) of sodium 4-hydroxybenzenesulfonate, dissolved in 500ml of anhydrous methanol. Slowly add 108g of sodium methoxide methanol solution (30wt%) with stirring. After the addition is complete, stir at room temperature for 30 minutes. Slowly add 108.9g (0.9mol) of allyl bromide, and reflux at 70℃ for 8 hours. After cooling the reaction system, filter under vacuum. Wash the solid with a small amount of anhydrous methanol to obtain crude sodium p-allyloxybenzenesulfonate. Recrystallize from deionized water to obtain 52.6g of purified sodium p-allyloxybenzenesulfonate (SAPE-Na), yield: 74%.
[0049] Step 2: Weigh 200g of strongly acidic cation exchange resin and soak it in saturated sodium chloride aqueous solution, wash it with deionized water, soak it in hydrochloric acid, and wash it with deionized water until neutral. Dissolve 40g of sodium p-allyloxybenzenesulfonate (SAPE-Na) in 800ml of deionized water and pass it through the strongly acidic cation exchange resin twice. Before each use, the strongly acidic cation exchange resin should be soaked in hydrochloric acid solution and washed with deionized water until neutral. Collect the effluent after passing sodium p-allyloxybenzenesulfonate through the ion exchange resin, concentrate it to obtain 33g of p-allyloxybenzenesulfonic acid (SAPE-H), yield: 91%.
[0050] Step 3: Dissolve 21.4 g of p-allyloxybenzenesulfonic acid (SAPE-H) in 200 ml of ethanol solution, add 1.2 equivalents of lithium hydroxide, stir at room temperature for 12 h, filter to remove insoluble matter, evaporate the filtrate to dryness to obtain a white solid, dry under vacuum at 60 °C for 4 h, selectively dissolve the product with a large amount of isopropanol, filter to remove insoluble impurities, evaporate the filtrate to dryness to obtain a white solid, dry under vacuum at 60 °C for 8 h to obtain 18.0 g of product p-allyloxybenzenesulfonic acid lithium (SAPE-Li). Yield: 82%, purity ≥99.9%, moisture ≤500 ppm.
[0051] Example 2
[0052] Step 1: Purge a 2L four-necked flask with nitrogen for 15 min to remove air from the reaction system, replacing it with a nitrogen atmosphere. Add 116.4 g (0.6 mol) of sodium 4-hydroxybenzenesulfonate and 1000 mL of anhydrous methanol. Slowly add 216 g of sodium methoxide methanol solution (30 wt%) while stirring. After the addition is complete, stir at room temperature for 30 min. Slowly add 217.8 g (1.8 mol) of allyl bromide and reflux at 75 °C for 8 h. After the reaction system cools, filter under vacuum. Wash the solid with a small amount of anhydrous methanol to obtain crude sodium p-allyloxybenzenesulfonate. Recrystallize from deionized water to obtain 109 g of purified sodium p-allyloxybenzenesulfonate (SAPE-Na), yield: 77%.
[0053] Step 2: Weigh 200g of strong acid cation exchange resin and soak it in saturated sodium chloride aqueous solution, wash it with deionized water, soak it in hydrochloric acid, and wash it with deionized water until neutral. Dissolve 60g of sodium p-allyloxybenzenesulfonate (SAPE-Na) in 800ml of deionized water and pass it through the strong acid cation exchange resin twice. Before each use, the strong acid cation exchange resin should be soaked in hydrochloric acid solution and washed with deionized water until neutral. Collect the effluent after sodium p-allyloxybenzenesulfonate has passed through the ion exchange resin, concentrate it to obtain 48.4g of p-allyloxybenzenesulfonic acid (SAPE-H), yield: 89%.
[0054] Step 3: Dissolve 20g of p-allyloxybenzenesulfonic acid (SAPE-H) in 200ml of ethanol solution, add 0.55 equivalents of lithium carbonate, stir at room temperature for 12h, filter to remove insoluble matter, evaporate the filtrate to dryness to obtain a white solid, dry under vacuum at 60℃ for 4h, selectively dissolve the product with a large amount of isopropanol, filter to remove insoluble impurities, evaporate the filtrate to dryness to obtain a white solid, dry under vacuum at 60℃ for 8h to obtain 16g of white solid product p-allyloxybenzenesulfonic acid lithium (SAPE-Li). Yield: 77%, purity ≥99.9%, moisture ≤500ppm.
[0055] Example 3
[0056] Step 1: Purge a 2L four-necked flask with nitrogen for 15 min to remove air from the reaction system, replacing the atmosphere with nitrogen. Add 58.2g (0.3mol) sodium 4-hydroxybenzenesulfonate and 500ml anhydrous methanol. While stirring, slowly add 108g of sodium methoxide methanol solution (30wt%). After the addition is complete, stir at room temperature for 30 min. Slowly add 108.9g (0.9mol) allyl bromide, and reflux at 70℃ for 8 h. After cooling the reaction system, filter under vacuum. Wash the solid with a small amount of anhydrous methanol. Crude sodium p-allyloxybenzenesulfonate is obtained. Recrystallization from deionized water yields 52.6g of purified sodium p-allyloxybenzenesulfonate (SAPE-Na), with a yield of 74%.
[0057] Step 2: Weigh 200g of strong acid cation exchange resin and soak it in saturated sodium chloride aqueous solution, wash it with deionized water, and soak it in lithium oxalate aqueous solution and then wash it with deionized water to ensure that there is no lithium oxalate residue in the effluent.
[0058] Step 3: Dissolve 23.6g of sodium p-allyloxybenzenesulfonate (SAPE-Na) in 800ml of deionized water, and pass it twice through a lithium-treated, strongly acidic cation exchange resin. Before each use, the strongly acidic cation exchange resin must be soaked in a lithium oxalate aqueous solution and washed with deionized water to ensure that the effluent is free of lithium oxalate residue. Collect the effluent and evaporate to dryness to obtain crude p-allyloxybenzenesulfonate. Then, dissolve it in 70℃ hot ethanol until saturated, cool to crystallize, and vacuum dry at 60℃ to obtain 18g of purified p-allyloxybenzenesulfonate (SAPE-Li). Yield: 82%, purity ≥99.9%, moisture ≤500ppm.
[0059] The present invention has been described in detail above, with the aim of enabling those skilled in the art to understand and implement the invention. However, this description should not be construed as limiting the scope of protection of the invention. All equivalent changes or modifications made in accordance with the spirit and essence of the invention should be included within the scope of protection of the invention.
Claims
1. A method for preparing lithium p-allyloxybenzenesulfonate, characterized in that: Lithium p-allylbenzenesulfonate was prepared by subjecting sodium p-allylbenzenesulfonate to a strong acidic cation exchange resin and a lithium salt.
2. The method for preparing lithium p-allyloxybenzenesulfonate according to claim 1, characterized in that: The lithium salt is one or more of lithium hydroxide, lithium carbonate, lithium oxalate, and lithium chloride.
3. The method for preparing lithium p-allyloxybenzenesulfonate according to claim 1, characterized in that: The preparation method includes the following steps: (1) Dissolve the sodium p-allyloxybenzenesulfonate in deionized water and pass it through the strong acid cation exchange resin 1 to 3 times to obtain p-allyloxybenzenesulfonic acid. (2) Dissolve the p-allyloxybenzenesulfonic acid in alcohol or deionized water, add the lithium salt and react to obtain the lithium p-allyloxybenzenesulfonate.
4. The method for preparing lithium p-allyloxybenzenesulfonate according to claim 3, characterized in that: The strongly acidic cation exchange resin is activated before each use by soaking in hydrochloric acid and washing with deionized water until neutral.
5. The method for preparing lithium p-allyloxybenzenesulfonate according to claim 3, characterized in that: In step (2), the alcohol is methanol, ethanol, or a mixture of both; or, In step (2), the concentration of p-allyloxybenzenesulfonic acid dissolved in the alcohol or water is 0.4–0.6 mol / L; or, In step (2), the molar ratio of p-allyloxybenzenesulfonic acid to lithium ions in the lithium salt is 1:1.05–1.2; or, In step (2), the reaction is carried out at room temperature.
6. The method for preparing lithium p-allyloxybenzenesulfonate according to claim 1, characterized in that: The preparation method includes the following steps: (a) The strongly acidic cation exchange resin is soaked in saturated sodium chloride, washed with deionized water, soaked in lithium salt aqueous solution, and washed with deionized water until no lithium salt residue remains in the effluent; wherein the lithium salt is one or more of lithium hydroxide, lithium oxalate, and lithium chloride. (b) The sodium p-allyloxybenzenesulfonate is dissolved in deionized water and passed through a strongly acidic cation exchange resin treated in step (a) 1 to 3 times to obtain the lithium p-allyloxybenzenesulfonate; wherein the strongly acidic cation exchange resin is treated in step (a) before each use.
7. The method for preparing lithium p-allyloxybenzenesulfonate according to claim 3 or 6, characterized in that: The concentration of the sodium p-allyloxybenzenesulfonate dissolved in deionized water is 0.1–0.4 mol / L.
8. The method for preparing lithium p-allyloxybenzenesulfonate according to claim 3 or 6, characterized in that: After the reaction is completed, the product is purified by recrystallization or selective dissolution to obtain the lithium p-allyloxybenzenesulfonate. The solvent used for recrystallization is one or more of methanol, ethanol, and deionized water. The solvent used for selective dissolution is one or more of methanol, ethanol, isopropanol, n-butanol, tetrahydrofuran, and ethylene glycol dimethyl ether.
9. The method for preparing lithium p-allyloxybenzenesulfonate according to claim 1, characterized in that: The sodium p-allyloxybenzenesulfonate was prepared by reacting sodium 4-hydroxybenzenesulfonate with allyl bromide under reflux in the presence of sodium methoxide and solvent.
10. The method for preparing sodium allyl oxybenzenesulfonate according to claim 9, characterized in that: The molar ratio of sodium 4-hydroxybenzenesulfonate, sodium methoxide, and allyl bromide is 1:1 to 2:1 to 3; or, The reflux temperature is 60–80°C, and the reflux time is 4–12 hours; or, The solvent is one or more of methanol, ethanol, tetrahydrofuran, acetone, and dimethyl sulfoxide.