Quantitative analysis method of bis (chlorosulfonyl) imide acid
The quantitative analysis of bischlorosulfonylimide acid by alcohol derivatization combined with gas chromatography solved the problems of unclear reaction pathway and lack of monitoring methods in the synthesis process of bischlorosulfonylimide, achieved simultaneous detection of product purity and impurities, and improved the yield and stability of downstream products.
Patent Information
- Application Number
- CN202511256213.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-04
- Publication Date
- 2025-10-17
AI Technical Summary
The existing technology for the synthesis of bischlorosulfonyl imide has an unclear reaction path, a complex intermediate generation mechanism, many side reactions, and a lack of effective process monitoring methods, resulting in unstable yields and downstream product performance.
By using alcohol derivatization combined with gas chromatography (GC) or gas chromatography-mass spectrometry (GC-MS) analytical instruments, dynamic tracking and purity detection of raw materials and products can be achieved through derivatization reactions of dichlorothionyl, chlorosulfonic acid, and bischlorosulfonyl imide acid, and efficient detection methods are developed to meet the quality control needs of industrial production.
The precise monitoring of the bischlorosulfonyl imide synthesis reaction and the simultaneous analysis of product purity and trace impurities were achieved, which improved the stability of the yield and the performance of downstream products and met the quality control requirements of industrial production.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the field of analytical chemistry, and particularly relates to a quantitative analysis method of bischlorosulfonyl imide acid. BACKGROUND
[0002] Bischlorosulfonyl imide (chemical formula: Cl2S(O)2NH) is an important class of sulfonamide compounds, which is used as a precursor of high-performance lithium salt (such as LiFSI), an acidic assistant in organic catalytic reactions, and a core intermediate of sulfonamide functional materials, and has key application value in the fields of new energy, chemical industry and medicine.
[0003] However, its industrial application is highly dependent on the precise control of the synthesis reaction process and the efficient detection of product purity, which directly determines the yield, cost and performance of downstream products.
[0004] The traditional synthesis process of bischlorosulfonyl imide (such as sulfanilamide chlorination method, sulfuryl chloride ammonolysis method) has the following defects: the reaction path is not clear, the intermediate generation mechanism is complex, and the side reaction; the process monitoring means is scarce: raw materials and products will cause serious corrosion to gas chromatography (GC), liquid chromatography (LC), mass spectrometry (MS), so nuclear magnetic monitoring is usually used to monitor the remaining raw materials and product purity. However, the detection limit and accuracy of nuclear magnetic resonance will cause instability of yield and performance of downstream products.
[0005] In view of the above technical bottlenecks, the present application focuses on: 1. Precise monitoring of bischlorosulfonyl imide synthesis reaction process: through alcohol derivatization method to dynamically track raw materials dichloro sulfoxide, chlorosulfonic acid and product bischlorosulfonyl imide acid, which is helpful for precise optimization of process parameters; 2. Innovative design of efficient detection method: develop alcohol-based gas chromatography (GC) to realize synchronous analysis of product purity and trace impurities, and meet the quality control needs of industrial production. SUMMARY
[0006] In view of the above problems, the present application aims to provide a quantitative analysis method of bischlorosulfonyl imide acid.
[0007] To achieve the above purpose, the present application adopts the following technical scheme: A quantitative analysis method of bischlorosulfonyl imide acid, the process is as follows: (1) A certain amount of dichloro sulfoxide, chlorosulfonic acid, bischlorosulfonyl imide acid standard is taken respectively, diluted with an organic solvent, and then an excess of alcohol is added for derivatization reaction. After the derivatization reaction is completed, the yield W1 of the corresponding derivative product of dichloro sulfoxide, chlorosulfonic acid and bischlorosulfonyl imide acid is detected by an analytical instrument; (2) taking the dithio acid sample solution, diluting it with an organic solvent, adding an excess of alcohol to perform a derivatization reaction, and after the derivatization reaction is completed, detecting the purity W2 of the corresponding derivatization products of dithio sulfate, chlorosulfonic acid and dithio acid by using an analytical instrument, and W2 / W1 x 100% is the actual purity of dithio sulfate, chlorosulfonic acid and dithio acid.
[0008] Further, in steps (1) and (2), the analytical instrument used is gas chromatography (GC) or GC-MS.
[0009] Further, in steps (1) and (2), the alcohol is at least one of methanol, ethanol, pentanol and octanol, and the derivatization reaction time is 30-60 min.
[0010] Further, in steps (1) and (2), the organic solvent is dichloromethane, tetrahydrofuran, toluene, ethyl acetate, or a mixture of two or more of them in any proportion.
[0011] Further, in steps (1) and (2), the derivatization reaction temperature is 10-60°C.
[0012] Further, in step (1), the concentration of the dithio sulfate, chlorosulfonic acid and dithio acid standard in the organic solvent is 1-2 mol / L; and the amount of alcohol added is 1.1-1.5 times the molar amount of each substance.
[0013] Further, in step (1), the ratio of the organic solvent for the dithio acid sample solution is 0.1-0.5 g:1 mL.
[0014] Further, in steps (1) and (2), the GC detection conditions are as follows: chromatographic column: Agilent DB-1701 gas chromatographic column, vaporization chamber temperature 200-230°C, programmed temperature conditions: initial temperature 80°C, hold for 2 min, temperature increase rate 10°C / min, final temperature 200°C, hold for 5 min, detector temperature 230°C, split ratio 80:1, using octane as an internal standard.
[0015] Preferably, the reaction temperature is 40°C, the solvent is dichloromethane, and the alcohol is pentanol.
[0016] The purity of the dithio sulfate, chlorosulfonic acid and dithio acid standard is all ≥99%.
[0017] The present application has the following beneficial technical effects: compared with the conventional nuclear magnetic monitoring method, the progress of the synthesis reaction of bischlorosulfonamide is accurately monitored, and the purity and trace impurities of the product are simultaneously analyzed, meeting the quality control requirements of industrial production. Chlorosulfonic acid interferes with bischlorosulfonamide acid, and nuclear magnetic method cannot detect chlorosulfonic acid within 20%. BRIEF DESCRIPTION OF DRAWINGS
[0018] Figure 1 is the gas chromatogram of the sample of embodiment 2 of the present application. DETAILED DESCRIPTION
[0019] The following examples merely provide a complete disclosure of how the compounds, compositions, articles, devices, and / or methods described and claimed herein can be made and evaluated, and are intended to be purely exemplary and are not intended to be limiting to the scope of the inventors' claimed application. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in degrees C, and pressure is at or near atmospheric.
[0020] Example 1 The derivation yield of dichlorosulfoxide, chlorosulfonic acid, bischlorosulfonamide acid standard was determined, and the process was as follows: 1 mol of dichlorosulfoxide, chlorosulfonic acid, and bischlorosulfonamide acid standard with a purity of 99% were respectively diluted with dichloromethane to 1 mol / L, 1.2 times the molar amount of pentanol was added to each substance, and the product was sampled for GC detection after stirring at 40℃ for 30-60 min. The detection conditions were as follows: Agilent DB-1701 gas chromatography column, injection amount: 1 μL, vaporization chamber temperature 210℃, programmed temperature conditions: initial temperature 80℃, high-purity nitrogen as carrier gas, flow rate 50 mL / min, holding time 2 min, temperature rising rate 10℃ / min, final temperature 200℃, holding time 5 min, detector temperature 230℃, split ratio 80:1, running time 15 min. Two groups of parallel samples were prepared, octane was used as an internal standard, and the internal standard method was used to determine the proportion of the product.
[0021] The calculation formula is as follows: w 样 is the mass proportion of the sample, with a unit of %; A 样 is the peak area value of the sample in GC detection; m 样 is the sampling amount of the sample in GC detection, with a unit of g; A 标 is the peak area value of the internal standard in GC detection; m 标The sampling amount of the internal standard in GC detection is g; f is a correction factor, and the formula is 0.1 g of the internal standard and the sample are mixed and diluted to 10 g to obtain a constant correction factor, which is brought into the above formula.
[0022] A 内 The peak area value of the internal standard; m 内 The specific mass of the internal standard; A1 is the peak area value of the sample; m1 is the specific mass of the sample.
[0023] The specific results are shown in Table 1.
[0024] Table 1: Detection results of Example 1 As shown in Table 1, the yields of dichlorosulfoxide, chlorosulfonic acid and bischlorosulfonyl imide acid determined by the internal standard are 98%, 96% and 99% respectively. Bischlorosulfonyl imide acid has the best response effect.
[0025] Example 2 The verification of the accuracy of the method of the present application is as follows: Dichlorosulfoxide, chlorosulfonic acid and bischlorosulfonyl imide acid with a purity of 99% are put into a solvent dichloromethane according to a molar ratio of 1:1:1, so that the concentration of bischlorosulfonyl imide acid is 1 mol / L, 1.2 times the total molar amount of the three is added pentanol, and the product is sampled for GC detection after stirring at 40℃ for 30-60 min. Three groups of parallel samples are prepared, each group is tested twice, octane is used as an internal standard, and the proportion of the product is determined by the internal standard. The test results are shown in Table 2.
[0026] Table 2: Detection results and calculation results of Example 1.
[0027] As shown in Table 2, the molar ratio of the derived products of dichlorosulfoxide, chlorosulfonic acid and bischlorosulfonyl imide acid after derivation is 0.96:0.94:1. Each group is tested twice, and the two test results are consistent. The molar ratio is divided by the derivation yield obtained in Table 1 to obtain the calculated derivation molar ratio of 0.98:0.98:1.01. Compared with the molar ratio of the raw materials, there is only a 2% deviation of dichlorosulfoxide and chlorosulfonic acid, and a 1% deviation of bischlorosulfonyl imide acid. This method can be used as a method for analyzing the control and bischlorosulfonyl imide.
[0028] Example 3 The verification of the accuracy of the method of the present application is as follows: The dichlorosulfoxide, chlorosulfonic acid and bis-dichlorosulfonyl imide acid are put into a solvent dichloromethane according to a molar ratio of 2:0.1:1, so that the concentration of the bis-dichlorosulfonyl imide acid is 1 mol / L, 1.2 times of the total molar amount of the three substances of pentanol is added, and the mixture is stirred at 10°C for 30-60 min. The product is sampled for GC detection. The molar ratio of the derivative is 2.03:0.09:0.99 determined by the internal standard method using octane as the internal standard. The repeatability deviation is less than 0.5%.
[0029] Example 4 The content of bis-dichlorosulfonyl imide acid, dichlorosulfoxide and chlorosulfonic acid in the bis-dichlorosulfonyl imide synthesis reaction process is detected according to the following process: 10 g of the bis-dichlorosulfonyl imide acid synthesis liquid on the production line is taken, 50 mL of dichloromethane is added, and the mixture is stirred uniformly and cooled to 10°C. 4.2 g of pentanol is added dropwise, and the mixture is reacted for 30 min. Three groups of parallel samples are prepared, octane is used as the internal standard, the average proportion of bis-dichlorosulfonyl imide acid is 70wt%, the proportion of bis-dichlorosulfonyl imide acid is 71wt% by dividing the derivatization yield of bis-dichlorosulfonyl imide acid in Table 1 by 99%, the average proportion of dichlorosulfoxide is 25wt%, the proportion of dichlorosulfoxide is 26% by dividing the derivatization yield of dichlorosulfoxide in Table 1 by 98%, and the average proportion of chlorosulfonic acid is 4wt%, the proportion of chlorosulfonic acid is 4wt% by dividing the derivatization yield of chlorosulfonic acid in Table 1 by 96%.
[0030] The above examples are the preferred embodiments of the present application, but the embodiments of the present application are not limited to the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application are equivalent replacement methods and are included in the protection scope of the present application.
Claims
1. A quantitative analysis method for bischlorosulfonyl imide acid, characterized in that: The process is as follows: (1) Take a certain amount of thionyl chloride, chlorosulfonic acid, and bis(chlorosulfonyl)imidic acid standard respectively, dilute them with an organic solvent, add an excess of alcohol to carry out a derivatization reaction, and after the derivatization reaction is completed, use an analytical instrument to detect the yield W1 of the corresponding derivative products of thionyl chloride, chlorosulfonic acid, and bis(chlorosulfonyl)imidic acid; (2) Take the bischlorosulfonyl imide acid solution to be tested, dilute it with an organic solvent, and then add an excess of alcohol to carry out a derivatization reaction. After the derivatization reaction is completed, use an analytical instrument to detect the purity W2 of the corresponding derivative products of thionyl chloride, chlorosulfonic acid, and bischlorosulfonyl imide acid. W2 / W1×100% is the actual purity of thionyl chloride, chlorosulfonic acid, and bischlorosulfonyl imide acid.
2. The quantitative analysis method of bischlorosulfonyl imide acid according to claim 1, wherein In step (1) and step (2), the analytical instrument used is gas chromatography (GC) or gas chromatography-mass spectrometry (GC-MS).
3. The quantitative analysis method of bischlorosulfonyl imide acid according to claim 1, wherein In step (1) and step (2), the alcohol is at least one of methanol, ethanol, pentanol and octanol, and the derivatization reaction time is 30 to 60 minutes.
4. The quantitative analysis method of bischlorosulfonyl imide acid according to claim 1, wherein In step (1) and step (2), the organic solvent is one or a mixture of two or more of dichloromethane, tetrahydrofuran, toluene, ethyl acetate and glycol dimethyl ether in any proportion.
5. The quantitative analysis method of bischlorosulfonyl imide acid according to claim 1, characterized in that: In step (1) and step (2), the temperature of the derivatization reaction is 10-60°C.
6. The quantitative analysis method of bischlorosulfonyl imide acid according to claim 1, characterized in that: In step (1), the concentration of thionyl chloride, chlorosulfonic acid, and bis(chlorosulfonyl)imide acid standards in the organic solvent is 1-2 mol / L; the amount of alcohol added is 1.1-1.5 times the molar amount of each substance.
7. The quantitative analysis method of bischlorosulfonyl imide acid according to claim 1, characterized in that: In step (1), the ratio of the bischlorosulfonyl imide acid test solution to the organic solvent is 0.1-0.5 g:1 mL.
8. The quantitative analysis method of bischlorosulfonyl imide acid according to claim 2, characterized in that: In step (1) and step (2), the GC detection conditions are as follows: vaporization chamber temperature 200~230℃, programmed temperature conditions: initial temperature 80℃, hold 2min, heating rate 10℃ / min, final temperature 200℃, hold 5min, detector temperature 230℃, split ratio 80:1, octane is used as internal standard.
9. The quantitative analysis method of bischlorosulfonyl imide acid according to claim 1, characterized in that: The purity of thionyl chloride, chlorosulfonic acid, and bis(chlorosulfonyl)imidic acid standards was ≥99%.