Analysis method for simultaneously detecting benzohydroxamic acid and 3-phenyl-1, 4, 2-dioxazole-5-ketone

Abstract

The invention discloses an analysis method for simultaneously detecting benzohydroxamic acid and 3-phenyl-1, 4, 2-dioxazole-5-ketone, which adopts a gas chromatographic method for detection, and adopts a weak-polarity SE-54 chromatographic column as a chromatographic column. The gas chromatography conditions are as follows: a heating procedure: the initial temperature is 50-70 DEG C, the temperature is kept for 1-2 minutes, and the temperature is raised to 260-280 DEG C at the rate of 40-50 DEG C / min; the temperature of a sample inlet is 260-300 DEG C; the temperature of the detector is 260-300 DEG C; the split ratio is (20: 1)-(100: 1); the column flow is 1 to 3 mL / min. The method can be used for analyzing and detecting the 3-phenyl-1, 4, 2-dioxazole-5-ketone and the benzohydroxamic acid which is not completely reacted in the production process, has the characteristics of rapidness, simplicity, accuracy and the like, and has important practical application value on reaction monitoring and quality control in the production process of the 3-phenyl-1, 4, 2-dioxazole-5-ketone.

Description

Technical Field

[0001] The invention relates to a gas chromatography analysis method for chemical substances, and in particular to an analysis method for simultaneously detecting benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one. Background Art

[0002] At present, the battery industry focuses on the research of high energy density and long cycle life of batteries, and pays more attention to the research of additives, especially the research on additives to improve the high temperature storage and long cycle performance of batteries. Dioxazolones have a wide range of uses and can be used in medicine, pesticides, polymer improvement, organic synthesis intermediates, etc. Among them, 3-phenyl-1,4,2-dioxazol-5-one (PDO) is an effective synthetic intermediate and is widely used in the preparation of other compounds in organic synthesis. Especially as a battery electrolyte additive, 3-phenyl-1,4,2-dioxazol-5-one forms a passivated SEI layer on the surface of the graphite electrode to improve the high temperature storage and cycle performance of the battery.

[0003] At present, the research on 3-phenyl-1,4,2-dioxazol-5-one is mostly focused on synthesis and application, and there is no report on the detection method of 3-phenyl-1,4,2-dioxazol-5-one. Therefore, how to quickly and effectively detect 3-phenyl-1,4,2-dioxazol-5-one has become a problem to be solved. In addition, while detecting 3-phenyl-1,4,2-dioxazol-5-one, the reaction raw material benzohydroxamic acid also needs to be detected to monitor whether the reaction is completed, so as to facilitate reaction monitoring and quality control of the production process of 3-phenyl-1,4,2-dioxazol-5-one. Summary of the invention

[0004] In order to solve the above technical problems, the purpose of the present invention is to provide an analytical method for simultaneously detecting benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one, which can analyze and detect 3-phenyl-1,4,2-dioxazol-5-one and benzohydroxamic acid that has not been completely reacted in the production process, and has the characteristics of rapidity, simplicity, accuracy, etc., and has important practical application value for reaction monitoring and quality control in the production process of 3-phenyl-1,4,2-dioxazol-5-one.

[0005] In order to achieve the above technical objectives and the above technical effects, the present invention is implemented through the following technical solutions:

[0006] An analytical method for simultaneously detecting benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one, using gas chromatography for detection, and the chromatographic column used is a weak polar SE-54 chromatographic column; the gas chromatography conditions are as follows:

[0007] Heating program: start at 50-70°C, hold for 1-2 min, and heat to 260-280°C at a rate of 40-50°C / min;

[0008] The injection port temperature is 260-300°C;

[0009] The detector is a hydrogen flame detector, and the detector temperature is 260-300°C;

[0010] Split ratio 20:1-100:1;

[0011] Hydrogen flow rate 30-50mL / min;

[0012] The column flow rate was 1-3 mL / min.

[0013] Furthermore, the specifications of the chromatographic column are 30m×0.32mm×0.25μm.

[0014] Furthermore, the gas chromatograph used in the analysis method is Agilent 8860.

[0015] Furthermore, the injection volume of the gas chromatography is 0.2-1 μL.

[0016] Furthermore, the analysis method uses an area normalization method to analyze the substance content.

[0017] Furthermore, when the area normalization method is used to analyze the substance content, the arithmetic mean of the three parallel determination results is taken as the reported result, and the relative standard deviation of the three parallel determination results of the sample is less than 5%. Furthermore, the gas chromatography conditions are preferably:

[0018] Heating program: starting temperature is 50°C, maintained for 2 min, and then heated to 280°C at a rate of 50°C / min;

[0019] The injection port temperature was 280°C;

[0020] The detector is a hydrogen flame detector, and the detector temperature is 280°C;

[0021] Split ratio 50:1;

[0022] Hydrogen flow rate 30mL / min;

[0023] The column flow rate was 3.0 mL / min.

[0024] In this analytical method, the resolution between benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one is greater than 1.5.

[0025] The beneficial effects of the present invention are:

[0026] The present invention adopts gas chromatography and uses a specific chromatographic column and gas chromatography conditions to analyze and detect 3-phenyl-1,4,2-dioxazole-5-one and benzohydroxamic acid that has not been completely reacted in the production process, and has the characteristics of rapidity, simplicity, accuracy, etc., and has important practical application value for reaction monitoring and quality control in the production process of 3-phenyl-1,4,2-dioxazole-5-one. The method can not only realize the qualitative and quantitative analysis of 3-phenyl-1,4,2-dioxazole-5-one, but also analyze and detect benzohydroxamic acid that has not been completely reacted in the production process, and can realize complete separation and analysis of benzohydroxamic acid and 3-phenyl-1,4,2-dioxazole-5-one within 5.5 minutes, and the separation degree is greater than 1.5. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is the blank solution chromatogram;

[0028] Figure 2 is the chromatogram of the benzohydroxamic acid standard sample solution on SE-54 in Example 1;

[0029] Figure 3 This is the chromatogram of the 3-phenyl-1,4,2-dioxazol-5-one standard sample solution on SE-54 in Example 1;

[0030] Figure 4 This is the chromatogram of the mixed standard solution in Example 2 on SE-54;

[0031] Figure 5 The chromatogram of the mixed standard solution in Example 3 on SE-54;

[0032] Figure 6 The chromatogram of the standard sample solution of p-benzohydroxamic acid in Comparative Example 1 on HP-5;

[0033] Figure 7 This is the chromatogram of the 3-phenyl-1,4,2-dioxazol-5-one standard sample solution on HP-5 in Comparative Example 1;

[0034] Figure 8 This is the chromatogram of the mixed standard solution in Comparative Example 2 on SE-54;

[0035] Fig. 9 This is the chromatogram of the mixed standard solution in Comparative Example 3 on SE-54;

[0036] Fig.10 It is the chromatogram of the test solution 1 on SE-54;

[0037] Fig.11 It is the chromatogram of the test solution 2 on SE-54;

[0038] Fig.12 This is the chromatogram of the test solution 3 on SE-54. DETAILED DESCRIPTION

[0039] The preferred embodiments of the present invention are described in detail below in conjunction with the accompanying drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making a clearer and more definite definition of the protection scope of the present invention.

[0040] The present invention provides an analytical method for simultaneously detecting benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one, which is detected by gas chromatography, and the chromatographic column used is a weak polar SE-54 chromatographic column; the gas chromatography conditions are as follows:

[0041] Column temperature program: start at 50-70°C, hold for 1-2 min, and increase to 260-280°C at a rate of 40-50°C / min;

[0042] The injection port temperature is 260-300°C;

[0043] The detector is a hydrogen flame detector, and the detector temperature is 260-300°C;

[0044] Split ratio 20:1-100:1;

[0045] Hydrogen flow rate 30-50mL / min;

[0046] The column flow rate was 1-3 mL / min.

[0047] Wherein, the specifications of the chromatographic column are 30m×0.32mm×0.25μm.

[0048] The gas chromatograph used in this analysis was Agilent 8860.

[0049] In this analytical method, the injection volume of the gas chromatograph is 0.2-1 μL.

[0050] This analytical method uses the area normalization method to analyze the substance content; when using the area normalization method to analyze the substance content, the arithmetic mean of the three parallel determination results is taken as the reported result, and the relative standard deviation of the three parallel determination results of the sample is less than 5%

[0051] The gas chromatography conditions of the analysis method are most preferably:

[0052] Heating program: starting temperature is 50°C, maintained for 2 min, and then heated to 280°C at a rate of 50°C / min;

[0053] The injection port temperature was 280°C;

[0054] The detector is a hydrogen flame detector, and the detector temperature is 280°C;

[0055] Split ratio 50:1;

[0056] Hydrogen flow rate 30mL / min;

[0057] The column flow rate was 3.0 mL / min.

[0058] In this analytical method, the resolution between benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one is greater than 1.5.

[0059] Specifically, the analytical method for simultaneously detecting benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one comprises the following steps:

[0060] S1, Preparation of standard sample solution

[0061] Take 0.05 g of standard samples of benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one, respectively, and dissolve them in ethyl acetate to prepare standard sample solutions;

[0062] S2, detection of standard sample solution

[0063] The detection needs to meet the following conditions: ethyl acetate: chromatographically pure, content ≥99.9%, chromatographic column: weak polar SE-54 chromatographic column, 30m×0.32mm×0.25μm; detector: hydrogen flame detector, 260-300℃; injection port temperature: 260-300℃; heating program: 50-70℃ for 1-2min, heating to 260-280℃ at a rate of 40-50℃ / min, and maintaining for 5min; hydrogen flow rate: 30-50mL / min; split ratio: 20:1-100:1;

[0064] S3, delete interference items: delete the solvent peak ethyl acetate in the chromatogram.

[0065] S4, result calculation: Calculate the component content using the area normalization method.

[0066] S5. In step S4, the arithmetic mean of the three parallel determination results is taken as the reported result, and the relative standard deviation of the three results is ≤5%.

[0067] Example 1

[0068] Take benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one standard sample solutions, load them separately, and perform gas chromatography analysis using Agilent 8860 gas chromatograph. The chromatographic column is a weak polar SE-54 chromatographic column (30m×0.32mm×0.25μm, Agilent). The initial temperature of the program is 50℃, maintained for 2min, and then heated to 280℃ at a rate of 50℃ / min, maintained for 5min. The injection port temperature is 280℃, the hydrogen flame detector temperature is 280℃, the hydrogen flow rate is 30mL / min, the air flow rate is 300mL / min; the carrier gas flow rate is 25mL / min, the split ratio is 50:1; the column flow rate is 3.0mL / min, and the injection volume is 1μL. Figure 2 and Figure 3 As shown, the gas chromatography results show that benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one can be well separated, and the response values ​​of the two substances are good, which can meet the actual detection needs.

[0069] Example 2

[0070] Take benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one standard sample solutions respectively, mix them in equal proportions, prepare mixed standard solution and load them for gas chromatography analysis. Use Agilent 8860 gas chromatograph, the chromatographic column is weak polar SE-54 chromatographic column (30m×0.32mm×0.25μm, Agilent), the initial temperature of the program is 50℃, keep it for 2min, and then heat it to 260℃ at a rate of 40℃ / min, and keep it for 5min. The injection port temperature is 280℃, the hydrogen flame detector temperature is 280℃, the hydrogen flow rate is 30mL / min, the air flow rate is 300mL / min; the carrier gas flow rate is 25mL / min, the split ratio is 80:1; the column flow rate is 3.0mL / min, and the injection volume is 1μL. Figure 4 As shown, the gas chromatography results show that benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one can be well separated, and the response values ​​of the two substances are good, which can meet the actual detection needs.

[0071] Example 3

[0072] Take benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one standard sample solutions respectively, mix them in equal proportions, prepare mixed standard solution and load them for gas chromatography analysis. Use Agilent 8860 gas chromatograph, the chromatographic column is weak polar SE-54 chromatographic column (30m×0.32mm×0.25μm, Agilent), the initial temperature of the program is 60℃, keep it for 2min, and then heat it to 280℃ at a rate of 50℃ / min, and keep it for 5min. The injection port temperature is 280℃, the hydrogen flame detector temperature is 280℃, the hydrogen flow rate is 30mL / min, the air flow rate is 300mL / min; the carrier gas flow rate is 25mL / min, the split ratio is 20:1; the column flow rate is 2.0mL / min, and the injection volume is 1μL. Figure 5 As shown, the gas chromatography results show that benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one can be well separated, and the response values ​​of the two substances are good, which can meet the actual detection needs.

[0073] Comparative Example 1

[0074] Benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one standard sample solutions were taken for gas chromatography analysis, using an Agilent 8860 gas chromatograph, the chromatographic column was a weak polar HP-5 column (30m×0.32mm×0.25μm, Agilent), the initial temperature of the program was 50℃, maintained for 2min, and then heated to 280℃ at a rate of 50℃ / min, maintained for 5min, the injection port temperature was 280℃, the hydrogen flame detector temperature was 280℃, the hydrogen flow rate was 30mL / min, the air flow rate was 300mL / min; the carrier gas flow rate was 25mL / min, the split ratio was 50:1; the column flow rate was 3.0mL / min, and the injection volume was 1μL. The results are as follows Figure 6 and Figure 7 As shown in the figure, although benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one can be separated, the two substances do not exist as single peaks in the chromatogram, but instead split into other impurity peaks, which is not conducive to quantitative analysis of the chromatography.

[0075] Comparative Example 2

[0076] Benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one standard sample solutions were mixed in equal proportions to prepare a mixed standard solution for sample loading and gas chromatography analysis using an Agilent 8860 gas chromatograph with a weakly polar SE-54 column (30m×0.32mm×0.25μm, Agilent). The initial temperature of the program was 50°C, maintained for 1 min, then heated to 280°C at a rate of 20°C / min and maintained for 5 min. The injection port temperature was 280°C, the detector temperature was 280°C; the hydrogen flow rate was 30mL / min, the air flow rate was 300mL / min; the carrier gas flow rate was 3.0mL / min, the split ratio was 60:1; the column flow rate was 2.0mL / min, and the injection volume was 1μL. The results showed that ( Figure 8 ), benzohydroxamic acid can be eluted from the chromatographic column, but 3-phenyl-1,4,2-dioxazol-5-one is strongly retained and remains in the column.

[0077] Comparative Example 3

[0078] Benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one standard sample solutions were taken separately, mixed in equal proportions, and mixed standard solutions were prepared for loading and gas chromatography analysis. Agilent 8860 gas chromatograph was used, and the chromatographic column was weak polar SE-54 (30m×0.32mm×0.25μm, Agilent). The initial temperature of the program was 50℃, maintained for 1min, and then heated to 280℃ at a rate of 50℃ / min, maintained for 5min, the injection port temperature was 280℃, the detector temperature was 280℃; the hydrogen flow rate was 30mL / min, the air flow rate was 300mL / min; the carrier gas flow rate was 3.0mL / min, the split ratio was 50:1; the column flow rate was 4.0mL / min, and the injection volume was 1μL. The results showed that ( Fig. 9 ), both substances can be eluted, but they overlap slightly in the chromatogram. Considering the tolerance of the chromatographic column, a high flow rate will cause greater damage to a narrow-bore chromatographic column, so this chromatographic condition is not considered.

[0079] Using the chromatographic conditions of Example 1, samples of unknown purity were tested. Samples were injected with test solutions 1, 2, and 3. The purity was evaluated by the area normalization method. The results are as follows: Fig.10 , Fig.11 , Fig.12 And as shown in Table 1.

[0080] Table 1 Sample test results

[0081] sample Retention time purity 1 5.024 98.7％ 2 5.106 99.7％ 3 5.026 97.9％

[0082] The methodological study of the analytical method of the present invention is as follows:

[0083] 1. Exclusive inspection

[0084] Take a blank solution (solvent only) and a standard sample solution, analyze and detect according to the chromatographic conditions of Example 1 above, and record the chromatogram. Figure 1 , the chromatograms of the standard sample solutions are shown in Figure 2 , Figure 3 ; It can be seen from the chromatographic results that under this chromatographic condition, the solvent and other impurities in the sample have almost no effect on the test results, indicating that the method has good specificity.

[0085] 2. Repeatability test

[0086] Benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one standard sample solutions were respectively taken, and the samples were injected six times continuously according to the chromatographic conditions of Example 1, and the chromatograms were recorded.

[0087] The experimental results showed that after six consecutive injections, the RSDs of the retention time and peak area of ​​benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one were less than 5%, indicating that the system had good adaptability.

[0088] In summary, the gas phase detection method of benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one provided by the present invention has good sensitivity, specificity and accuracy, and is simple to operate and efficient.

[0089] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. An analytical method for simultaneously detecting benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one, characterized in that: Gas chromatography was used for detection, and the chromatographic column used was a weak polar SE-54 chromatographic column; the gas chromatography conditions were as follows: Heating program: start at 50-70°C, hold for 1-2 min, and heat to 260-280°C at a rate of 40-50°C / min; The injection port temperature is 260-300°C; The detector is a hydrogen flame detector, and the detector temperature is 260-300°C; Split ratio 20:1-100:1; Hydrogen flow rate 30-50mL / min; The column flow rate was 1-3 mL / min.

2. The analytical method for simultaneous detection of benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one according to claim 1, characterized in that: The specifications of the chromatographic column are 30m×0.32mm×0.25μm.

3. The analytical method for simultaneous detection of benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one according to claim 1, characterized in that: The gas chromatograph used was Agilent 8860.

4. The analytical method for simultaneous detection of benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one according to claim 1, characterized in that: The injection volume for gas chromatography is 0.2-1 μL.

5. The analytical method for simultaneous detection of benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one according to claim 1, characterized in that: This analytical method uses the area normalization method to analyze the substance content.

6. The analytical method for simultaneous detection of benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one according to claim 5, characterized in that: When the area normalization method is used to analyze the substance content, the arithmetic mean of the three parallel determination results is taken as the reported result, and the relative standard deviation of the three parallel determination results of the sample is less than 5%.

7. The analytical method for simultaneous detection of benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one according to claim 1, characterized in that: The gas chromatography conditions were: Heating program: starting temperature is 50°C, maintained for 2 min, and then heated to 280°C at a rate of 50°C / min; The injection port temperature was 280°C; The detector is a hydrogen flame detector, and the detector temperature is 280°C; Split ratio 50:1; Hydrogen flow rate 30mL / min; The column flow rate was 3.0 mL / min.

8. The analytical method for simultaneous detection of benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one according to claim 1, characterized in that: The resolution of benzohydroxamic acid and 3-phenyl-1,4,2-dioxazol-5-one was greater than 1.5.

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