Analysis method of substituted benzene peroxide

Abstract

The invention belongs to the technical field of peroxide analysis, and provides a method for analyzing substituted benzene peroxide, which comprises the following step of: performing high performance liquid chromatography detection on a solution of substituted benzene peroxide to finish analysis. By adopting the method disclosed by the invention, the content of at least one of the m-chloroperoxybenzoic acid, the benzoyl peroxide and the tert-butyl peroxybenzoate is measured by an HPLC (High Performance Liquid Chromatography) method, so that the method has very high accuracy and precision, and the problem of decomposition of peroxide in the measurement process does not exist. The method provided by the invention is clear in principle, simple, efficient and accurate in result.

Description

Technical Field

[0001] The invention relates to the technical field of peroxide analysis, in particular to an analysis method for substituted benzene peroxides. Background Art

[0002] Organic peroxides are used as initiators in polymerization processes and strong oxidants in oxidation processes. They play a very important role in chemical production and are widely used in the fields of materials, medicine and pesticides. Commonly used substituted benzene peroxides include benzoyl peroxide, tert-butyl perbenzoate, m-chloroperbenzoic acid, etc.

[0003] At present, the content analysis of peroxides mainly adopts the iodine titration method. Since there are by-products and intermediates in the synthesis reaction of organic peroxides, the iodine titration method mainly detects the oxidizing property of the substance. In most cases, the intermediates and by-products of the peroxidation reaction also have certain oxidizing properties, which are difficult to distinguish during analysis and will interfere with the results. This interference will lead to the inability to effectively control the quality and safety of the product, and may also cause hidden dangers in the subsequent use process.

[0004] Therefore, it is necessary to develop a method for determining the peroxide content of substituted benzenes, especially an analytical method for a mixture containing multiple organic peroxides during the reaction process. Summary of the invention

[0005] The purpose of the present invention is to overcome the defects in the prior art and provide an analytical method for substituted benzene peroxides.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides an analytical method for substituted benzene peroxides, comprising the following steps:

[0008] The analysis was completed by subjecting the solution of substituted benzene peroxide to high performance liquid chromatography;

[0009] The concentration of the solution of substituted benzene peroxide is 0.4-1.2 mg / mL.

[0010] Preferably, the substituted benzene peroxide is one or more of m-chloroperbenzoic acid, benzoyl peroxide and tert-butyl perbenzoate.

[0011] Preferably, the mobile phase for high performance liquid chromatography detection comprises an aqueous stabilizer solution and a solvent;

[0012] The volume ratio of the stabilizer aqueous solution to the solvent is 10-20:80-90.

[0013] Preferably, the stabilizer comprises ammonium formate, ammonium acetate or ammonium propionate;

[0014] The concentration of the stabilizer aqueous solution is 4 to 7 mmol / L; the pH of the stabilizer aqueous solution is 3 to 6;

[0015] The solvent was acetonitrile.

[0016] Preferably, the detection wavelength of the HPLC detection is 220-245 nm.

[0017] Preferably, the flow rate of the HPLC detection is 0.7-1 mL / min.

[0018] Preferably, the column temperature of the HPLC detection is 15-25°C.

[0019] Preferably, the injection volume of the HPLC detection is 1 to 5 μL.

[0020] The present invention provides an analysis method for substituted benzene peroxides, comprising the following steps: subjecting a solution of substituted benzene peroxides to high performance liquid chromatography detection to complete the analysis. The method of the present invention is used to measure the content of at least one of m-chloroperbenzoic acid, benzoyl peroxide and tert-butyl perbenzoate by HPLC, with high accuracy and precision, and there is no problem of decomposition of peroxides during the measurement process. The method provided by the present invention has a clear principle, is simple and efficient, and has accurate results. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The chromatogram of the chloroperbenzoic acid standard sample in Example 1;

[0022] Figure 2 The standard curve of chloroperbenzoic acid in Example 1 is shown;

[0023] Figure 3 The chromatogram of the chloroperbenzoic acid test sample in Example 1;

[0024] Figure 4 It is the chromatogram of the benzoyl peroxide standard sample in Example 2;

[0025] Figure 5 It is the chromatogram of the tert-butyl perbenzoate standard sample in Example 3. DETAILED DESCRIPTION

[0026] The present invention provides an analytical method for substituted benzene peroxides, comprising the following steps:

[0027] The analysis was completed by subjecting the solution of substituted benzene peroxide to high performance liquid chromatography;

[0028] The concentration of the substituted benzene peroxide solution is 0.4 to 1.2 mg / mL, preferably 0.5 to 1.1 mg / mL, more preferably 0.6 to 1 mg / mL, and even more preferably 0.7 to 0.8 mg / mL.

[0029] In the present invention, the solvent of the solution of substituted benzene peroxide is acetonitrile or methanol.

[0030] In the present invention, the substituted benzene peroxide is one or more of m-chloroperbenzoic acid, benzoyl peroxide and tert-butyl perbenzoate.

[0031] In the present invention, the mobile phase for high performance liquid chromatography detection comprises a stabilizer aqueous solution and a solvent.

[0032] In the present invention, the volume ratio of the aqueous stabilizer solution to the solvent is preferably 10-20:80-90, more preferably 12-18:82-88, and even more preferably 14-16:84-86.

[0033] In the present invention, the stabilizer comprises ammonium formate, ammonium acetate or ammonium propionate.

[0034] In the present invention, the concentration of the stabilizer aqueous solution is preferably 4-7 mmol / L, more preferably 4.5-6.5 mmol / L, more preferably 5-6 mmol / L; the pH of the stabilizer aqueous solution is preferably 3-6, more preferably 3.5-5.5, more preferably 4-5; the pH of the stabilizer aqueous solution is adjusted using an organic acid corresponding to the ammonium salt.

[0035] In the present invention, the solvent is acetonitrile.

[0036] In the present invention, the chromatographic column for high performance liquid chromatography detection is a reverse phase C18 chromatographic column.

[0037] In the present invention, the detection wavelength of the HPLC detection is preferably 220 to 245 nm, more preferably 225 to 240 nm, and even more preferably 230 to 235 nm.

[0038] In the present invention, the flow rate of the HPLC detection is preferably 0.7 to 1 mL / min, more preferably 0.75 to 0.95 mL / min, and even more preferably 0.8 to 0.9 mL / min.

[0039] In the present invention, the column temperature of the HPLC detection is preferably 15 to 25°C, more preferably 16 to 24°C, and even more preferably 18 to 22°C.

[0040] In the present invention, the injection volume of the HPLC detection is preferably 1 to 5 μL, more preferably 1.5 to 4.5 μL, and even more preferably 2 to 3 μL.

[0041] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0042] Example 1

[0043] Preparation of standard curve of m-chloroperbenzoic acid

[0044] The chromatographic column is a reverse phase C18 column, Syncronis C18, with a specification of 250 mm*4.6 mm*5 μm.

[0045] Ammonium formate was used to prepare a 5 mmol / L aqueous stabilizer solution, and formic acid was used to adjust the pH to 5; then the aqueous stabilizer solution and acetonitrile were prepared into a mobile phase in a ratio of 20:80.

[0046] The detection wavelength was 236 nm, the flow rate was 1 mL / min, the column temperature was 20 °C, and the injection volume was 5 μL.

[0047] Accurately weigh 20, 30, 40, 50, and 60 mg of meta-chloroperbenzoic acid standard substance, respectively, place them in a 50 mL volumetric flask, and dilute to the scale with acetonitrile to prepare meta-chloroperbenzoic acid solutions with concentrations of 0.4, 0.6, 0.8, 1.0, and 1.2 mg / mL.

[0048] The standard sample of m-chloroperbenzoic acid solution (concentration of 85%) was analyzed by high performance liquid chromatography. The spectrum is as follows: Figure 1 shown.

[0049] Different concentrations of m-chloroperbenzoic acid solutions were tested in turn under the same conditions, and the concentration (X) was linearly regressed against the peak area (Y) in the spectrum to obtain the linear regression equation Y = 9085.7X + 370.2 (R 2 =0.9990). The standard curve is as follows Figure 2 As shown, from Figure 2 It can be seen that the mass concentration of meta-chloroperbenzoic acid in the range of 0.4-1.2 mg / mL has a good linear relationship with the peak area.

[0050] Accurately weigh 30 mg of m-chloroperbenzoic acid, place it in a 50 mL volumetric flask, dilute it to the mark with acetonitrile and shake well, as the test solution. The test solution was injected according to the above conditions. The HPLC analysis result is as shown in the figure. Figure 3 As shown, from Figure 3 It can be seen that the peak shape of m-chloroperoxybenzoic acid is good and the peak is eluted quickly, taking only about 3.3 minutes. The peroxidation intermediate 14' and the hydrolysis byproduct 1.9' in the synthesis process are also well separated under this method.

[0051] System Precision Test for the Determination of Meta-Chloroperbenzoic Acid

[0052] 20, 40 and 60 mg of meta-chloroperbenzoic acid standard substance were accurately weighed respectively and placed in a 50 mL volumetric flask. The volume was made up to the mark with acetonitrile to prepare low, medium and high concentration meta-chloroperbenzoic acid solutions of 0.4, 0.8 and 1.2 mg / mL. The low, medium and high concentration meta-chloroperbenzoic acid solutions were tested in turn under the same conditions. Each concentration was repeated 6 times, the peak area was recorded, and the relative standard deviation was calculated. The results are shown in Table 1.

[0053] Table 1 System precision test results

[0054]

[0055] According to Table 1, the peak area RSD% of the low, medium and high concentration meta-chloroperbenzoic acid solutions were repeated 6 times and were 0.08%, 0.13% and 0.12% respectively, which meets the requirement of RSD% < 2% in the pharmacopoeia, indicating that the system has good repeatability, good precision and high test credibility.

[0056] Spike Test for Determination of Meta-Chloroperbenzoic Acid

[0057] Solution preparation:

[0058] Weigh 5 portions of meta-chloroperbenzoic acid sample: 25.36 mg, 25.21 mg, 25.62 mg, 24.95 mg, 25.41 mg, and place them in a 50 mL volumetric flask. Then add 37.20 mg, 28.70 mg, 18.93 mg, 15.91 mg, 9.96 mg of meta-chloroperbenzoic acid standard, respectively. Add acetonitrile to the scale and record them as 1, 2, 3, 4, 5 in sequence. Shake well and set aside.

[0059] The m-chloroperbenzoic acid spiked solutions with different concentrations were tested in turn under the same conditions, and the recovery rates were calculated. The results are shown in Table 2.

[0060] Table 2 Spike test results

[0061]

[0062] According to Table 2, the average recovery of m-chloroperbenzoic acid spiked solutions with different concentrations was 97.6%, and the RSD was 1.8%, indicating that the system had good accuracy.

[0063] Example 2

[0064] Determination of benzoyl peroxide content

[0065] The chromatographic column is a reverse phase C18 column, Syncronis C18, with a specification of 250 mm*4.6 mm*5 μm.

[0066] Ammonium acetate was used to prepare a 6 mmol / L aqueous stabilizer solution, and acetic acid was used to adjust the pH to 3; then the aqueous stabilizer solution and acetonitrile were prepared into a mobile phase in a ratio of 10:90.

[0067] The detection wavelength was 240 nm, the flow rate was 0.8 mL / min, the column temperature was 18 °C, and the injection volume was 3 μL.

[0068] Accurately weigh 30 mg of benzoyl peroxide, place it in a 50 mL volumetric flask, dilute it to the mark with acetonitrile and shake it well. This is used as the test solution. The test solution is injected. The HPLC analysis result is as shown in the figure below. Figure 4 As shown, according to Figure 4 It can be seen that benzoyl peroxide has a good peak shape and a fast peak emission, which takes only about 6.9 minutes.

[0069] Example 3

[0070] Determination of tert-butyl perbenzoate content

[0071] The chromatographic column is a reverse phase C18 column, Syncronis C18, with a specification of 250 mm*4.6 mm*5 μm.

[0072] Ammonium propionate was used to prepare a 4 mmol / L stabilizer aqueous solution, and propionic acid was used to adjust the pH to 4; then the stabilizer aqueous solution and acetonitrile were configured into a mobile phase in a ratio of 15:85.

[0073] The detection wavelength was 225 nm, the flow rate was 0.9 mL / min, the column temperature was 23 °C, and the injection volume was 1 μL.

[0074] Accurately weigh 30 mg of tert-butyl perbenzoate, place it in a 50 mL volumetric flask, dilute it to the mark with acetonitrile and shake it well. This is used as the test solution. The test solution is injected. The HPLC analysis result is as shown in the figure below. Figure 5 As shown, according to Figure 5 It can be seen that the peak shape of tert-butyl perbenzoate is good and the peak emerges quickly, taking only about 5.6 minutes.

[0075] Comparative Example

[0076] Determination of m-chloroperbenzoic acid by HPLC and iodine titration

[0077] The HPLC test conditions were the same as those in Example 1.

[0078] Accurately weigh 30 mg of m-chloroperbenzoic acid, place it in a 50 mL volumetric flask, dilute to the scale with acetonitrile and shake well to use as the test solution.

[0079] The content of m-chloroperbenzoic acid calculated according to the standard curve of Example 1 was 70.3%.

[0080] The meta-chloroperbenzoic acid sample was titrated according to the iodine titration method and the result was 76.5%.

[0081] It can be seen that the content of m-chloroperbenzoic acid sample determined by iodine titration method is higher than that by HPLC.

[0082] As can be seen from the above embodiments, the present invention provides an analytical method for substituted benzene peroxides, comprising the following steps: subjecting a solution of substituted benzene peroxides to high performance liquid chromatography detection to complete analysis. The method of the present invention is used to measure the content of at least one of m-chloroperbenzoic acid, benzoyl peroxide and tert-butyl perbenzoate by HPLC, with high accuracy and precision, and there is no problem of peroxide decomposition during the measurement process. The test result is accurate, which has obvious advantages over the iodine titration method.

[0083] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for analyzing substituted benzene peroxides, characterized in that: It includes the following steps: The analysis was completed by subjecting the solution of substituted benzene peroxide to high performance liquid chromatography; The concentration of the solution of substituted benzene peroxide is 0.4-1.2 mg / mL.

2. The method for analyzing substituted benzene peroxides according to claim 1, wherein: The substituted benzene peroxide is one or more of m-chloroperbenzoic acid, benzoyl peroxide and tert-butyl perbenzoate.

3. The analytical method for substituted benzene peroxides according to claim 2, wherein: The mobile phase for high performance liquid chromatography detection comprises an aqueous stabilizer solution and a solvent; The volume ratio of the stabilizer aqueous solution to the solvent is 10-20:80-90.

4. The analytical method for substituted benzene peroxides according to claim 3, wherein: The stabilizer comprises ammonium formate, ammonium acetate or ammonium propionate; The concentration of the stabilizer aqueous solution is 4 to 7 mmol / L; the pH of the stabilizer aqueous solution is 3 to 6; The solvent was acetonitrile.

5. The method for analyzing substituted benzene peroxides according to any one of claims 1 to 4, characterized in that: The detection wavelength of the high performance liquid chromatography detection is 220 to 245 nm.

6. The method for analyzing substituted benzene peroxides according to claim 5, wherein: The flow rate of the high performance liquid chromatography detection is 0.7 to 1 mL / min.

7. The method for analyzing substituted benzene peroxides according to claim 6, wherein: The column temperature of the high performance liquid chromatography detection is 15-25°C.

8. The method for analyzing substituted benzene peroxides according to claim 7, wherein: The injection volume of the high performance liquid chromatography detection is 1 to 5 μL.

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