A method for detecting the content of active ingredients in a perfluoroaryl borate solution

Abstract

This invention provides a method for detecting the content of active ingredients in perfluoroaryl boronic acid (PFAO) solutions. The method includes: dissolving an N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)boronic acid sample in a first and second organic solvent to obtain a test solution; detecting the test solution using high-performance liquid chromatography (HPLC) with two standards; qualitatively comparing the retention times of the test solution with the first and second standards; and determining the content of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)boronic acid in the test solution using an external standard method. This method provides complete separation of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)boronic acid and related impurities. The method offers high precision, accurate results, simple quantitative analysis, and good repeatability.

Description

Technical Field

[0001] This invention belongs to the technical field of component detection in organic compounds, and relates to a method for detecting the content of active ingredients in perfluoroarylborate solutions. Background Technology

[0002] Perfluoroaryl borates are a new generation of cocatalysts for metallocene catalysts, also known as ion activators. The main products are tetra(pentafluorophenyl)-substituted borates [B(C6F5)4]. － These are compounds whose cations are inorganic or organic ammonium ions, including potassium tetra(pentafluorophenyl)borate, sodium tetra(pentafluorophenyl)borate, triphenylcarbium tetra(pentafluorophenyl)borate, and N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate. Compared with methylaluminoxane (MAO), these borates exhibit highly efficient catalytic activity and have broader application prospects.

[0003] Currently, another perfluoroaryl boronic acid salt product is N,N-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate. This compound is a novel substance and currently has no CAS Registry number. It is an extremely viscous liquid at room temperature, and due to the inconvenience of storage and use, commercial production typically delivers it in solution form, using hexane or heptane as common solvents. There is currently no effective analytical method to accurately determine its content, and no standard is available. Existing analytical methods for similar compounds, such as N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, are not applicable. Accurately quantifying its anion and cation content is a crucial factor in production process monitoring and finished product quality management. Summary of the Invention

[0004] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide a method for detecting the content of active ingredients in perfluoroaryl boronic acid borate solutions. Using a three-eluent mobile phase and employing a dual-standard external standard method, the method effectively and accurately determines the content of anions and cations in N,N-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)boronic acid borate solutions, which are perfluoroaryl boronic acid borate products, thereby achieving quality control of N,N-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)boronic acid borate.

[0005] To achieve the above and other related objectives, the present invention provides a method for detecting the content of active ingredients in a perfluoroaryl boronic acid solution, comprising: dissolving an N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)boronic acid sample in a first organic solvent and a second organic solvent to obtain a test solution; detecting the test solution using high performance liquid chromatography with dual standards; qualitatively comparing the retention times of the test solution with the first and second standards; and determining the content of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)boronic acid in the test solution using an external standard method.

[0006] Preferably, the N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate sample is a hexane solution containing N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate.

[0007] Preferably, the chemical structural formula of the N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate is shown in formula (1) below.

[0008] Equation (1) is:

[0009] Preferably, the first organic solvent is selected from one of dimethylformamide (DMF, CAS No. 68-12-2), dimethylacetamide (DMAC, CAS No. 127-19-5), or dimethyl sulfoxide (DMSO, CAS No. 67-68-5).

[0010] Preferably, the second organic solvent is selected from dichloromethane, n-hexane, or n-heptane.

[0011] Preferably, the ratio of the mass (g) of the N,N,-bis(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate sample added to the volume (mL) of the first organic solvent added is 0.1-0.5:5, more preferably 0.15:5.

[0012] Preferably, the ratio of the mass (g) of the N,N,-bis(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate sample added to the volume (mL) of the second organic solvent added is 0.1-0.5:45, more preferably 0.15:45.

[0013] Preferably, the detection using dual standards via high-performance liquid chromatography includes the following steps:

[0014] 1) Divide the dual standards into a first standard and a second standard. Dissolve the first standard and the second standard in a first organic solvent and then dilute to a final volume to prepare a first standard solution and a second standard solution.

[0015] 2) High-performance liquid chromatography (HPLC) was used to detect the test solution, the first standard solution and the second standard solution in step 1) respectively. The retention times were compared for qualitative analysis. The peak position of the cation of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate in the test solution was determined by the first standard solution, and the peak position of the anion of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate in the test solution was determined by the second standard solution. Then, the external standard method was used for quantification to determine the content of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate composed of cations and anions in the test solution.

[0016] Preferably, in step 1), the first standard is N,N,-bis(hexadecyl)aniline (CAS No. 77772-74-8).

[0017] Preferably, in step 1), the second standard is N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate (CAS No. 118612-00-3).

[0018] Preferably, in step 1), the first organic solvent is selected from one of dimethylformamide (DMF, CAS No. 68-12-2), dimethylacetamide (DMAC, CAS No. 127-19-5), or dimethyl sulfoxide (DMSO, CAS No. 67-68-5).

[0019] Preferably, in step 1), the second organic solvent is selected from one of dichloromethane, n-hexane, or n-heptane.

[0020] Preferably, in step 1), the ratio of the mass (g) of the first standard added to the volume (ml) of the first organic solvent added and the volume (ml) of the second organic solvent added in the first standard solution is 0.02-0.1:5:45.

[0021] Preferably, in step 1), the ratio of the mass (g) of the second standard added to the volume (ml) of the first organic solvent added and the volume (ml) of the second organic solvent added in the second standard solution is 0.02-0.1:5:45.

[0022] Preferably, in step 2), the detector used in the high performance liquid chromatography is an ultraviolet detector (UV).

[0023] Preferably, in step 2), the high-performance liquid chromatography (HPLC) uses a C8 column (15-25cm × 0.46mm, 3.5-5μm; column length × inner diameter, stationary phase film thickness). The column is packed with octaalkylsilane-bonded silica gel.

[0024] More preferably, the chromatographic column is a CAPCELL PAK C8 column (15cm × 0.46mm, 5μm; column length × inner diameter, stationary phase film thickness). The CAPCELL PAK C8 column is manufactured by Shiseido Corporation of Japan, catalog number: Cat.No.90984. The column uses octaalkylsilane-bonded silica gel as packing material.

[0025] Preferably, in step 2), the column temperature used in the high-performance liquid chromatography is 30-50°C. More preferably, the column temperature is 40°C.

[0026] Preferably, in step 2), the injection volume used in the high-performance liquid chromatography is 2.0-10.0 μL. More preferably, the injection volume is 5.0 μL.

[0027] Preferably, in step 2), the flow rate used in the high-performance liquid chromatography is 0.8-1.2 mL / min. More preferably, the flow rate is 1.0 mL / min.

[0028] Preferably, in step 2), the detection wavelength used in the high-performance liquid chromatography is 205-215 nm. More preferably, the detection wavelength is 212 nm.

[0029] Preferably, in step 2), the mobile phase in the high performance liquid chromatography is 1-5 mM ammonium acetate aqueous solution-acetonitrile-isopropanol, wherein phase A is 1-5 mM ammonium acetate aqueous solution, phase B is acetonitrile, phase C is isopropanol, and the analysis time is 40 min; gradient elution is used.

[0030] More preferably, in the high performance liquid chromatography method, the mobile phase is 2mM ammonium acetate aqueous solution-acetonitrile-isopropanol, wherein phase A is 2mM ammonium acetate aqueous solution, phase B is acetonitrile, and phase C is isopropanol, and the analysis time is 40 min; gradient elution is used.

[0031] The above mM refers to mmol / L.

[0032] More preferably, as shown in Table 1, the specific procedure for gradient elution is as follows:

[0033] From 0 to 10 minutes, the volume ratio of phase A: phase B: phase C is 50:50:0-0:100:0;

[0034] 10-15 min, the volume ratio of phase A: phase B: phase C is 0:100:0-0:45:55;

[0035] For 15-40 minutes, the volume ratio of phase A: phase B: phase C is 0:45:55-0:45:55.

[0036] Table 1

[0037]

[0038] Preferably, in step 2), the external standard method includes the following steps:

[0039] A) Prepare a series of first and second standard solutions of different concentrations according to step 1), perform HPLC detection on each solution, obtain the linear relationship between the chromatographic peak area and corresponding content of the first standard in the first standard solution and the linear relationship between the chromatographic peak area and corresponding content of the second standard in the second standard solution, perform linear fitting on each solution, and calculate the regression equation of the standard working curve of the first standard and the regression equation of the standard working curve of the second standard.

[0040] B) Perform HPLC analysis on the test solution to obtain the chromatographic peak area of ​​the cation of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate. Substitute this peak area into the regression equation of the standard working curve of the first standard in step A). ​​Substitute this peak area into the regression equation of the standard working curve of the second standard in step A). ​​Calculate the content of the cation and anion of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate in the test solution.

[0041] More preferably, in the standard working curve of the first standard, the chromatographic peak area of ​​the first standard is used as the vertical axis (Y-axis), and its corresponding content (i.e., concentration) is used as the horizontal axis (X-axis); in the standard working curve of the second standard, the chromatographic peak area of ​​the second standard is used as the vertical axis (Y-axis), and its corresponding content (i.e., concentration) is used as the horizontal axis (X-axis).

[0042] Preferably, in step 2), the external standard method is used to calculate according to formula (1).

[0043] The formula (1) is: wi=[(Ai-b) / a] / c×100%,

[0044] Wherein, wi is the cation or anion content (i.e., concentration) of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate in the test solution; Ai is the chromatographic peak area of ​​the cation or anion of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate in the test solution; b is the intercept of the standard working curve of the first or second standard; a is the slope of the standard working curve of the first or second standard; and c is the sample volume of the test solution, in g.

[0045] The water used above is pure water.

[0046] As described above, the present invention provides a method for detecting the content of active ingredients in a perfluoroaryl boronic acid (PFAO) solution. By using two types of organic solvents for dissolution, it can achieve complete separation of the PFAO compound N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate from its related impurities. Simultaneously, this detection method uses three eluents as the mobile phase and employs a dual-standard external standard method to effectively detect the content of anions and cations in N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate, thereby enabling effective quality control of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate. This detection method exhibits good precision and accuracy, and the detection results are accurate, correctly reflecting the quality of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate, which is of great significance for monitoring the quality of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate. Attached Figure Description

[0047] Figure 1 The image shown is a liquid chromatogram of the determination of the first standard solution in this invention, where a is the first standard.

[0048] Figure 2 The image shown is a liquid chromatogram for determining the second standard solution in this invention, where b represents the tetratetrafluorophenyl)boron ion [B(C6F5)4] in the second standard. － ].

[0049] Figure 3 The image shows a liquid chromatogram of the test solution determined in this invention, where b is the anion of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate, and its retention time is related to... Figure 2 b is similar; c is the cation of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate, and its retention time is similar to... Figure 1 The a in the middle is similar.

[0050] Figure 4 The diagram shown is a standard working curve of the first standard sample in this invention.

[0051] Figure 5 The diagram shows the standard operating curve of the second standard in this invention. Detailed Implementation

[0052] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the present invention.

[0053] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0054] It should be noted that the process equipment or apparatus not specifically specified in the following embodiments are all conventional equipment or apparatus in the art; all pressure values ​​and ranges refer to relative pressure.

[0055] Furthermore, it should be understood that the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps, does not preclude the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps, unless otherwise stated. It should also be understood that the combined connection relationship between one or more devices / apparatus mentioned in this invention does not preclude the existence of other devices / apparatus before or after the combined devices / apparatus, or the insertion of other devices / apparatus between these explicitly mentioned devices / apparatus, unless otherwise stated. Moreover, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not for limiting the order of the method steps or limiting the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention.

[0056] The reagents and instruments used in the following examples are as follows:

[0057] 1. Reagents

[0058] Sample: N,N,-Di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate (developed and produced by Shanghai Kangpeng Technology Co., Ltd.).

[0059] Standards: N,N,-Di(hexadecyl)aniline (purity 99.9%, Shanghai Shuangfu Biotechnology Co., Ltd.); N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate (purity 99.5%, TCI (Shanghai) Chemical Industry Development Co., Ltd.).

[0060] Reagents: Dimethylformamide, dimethylacetyl, dimethyl sulfoxide (chromatographic grade, Sigma-Aldrich); dichloromethane, n-hexane, n-heptane (chromatographic grade, Shanghai Anpu Experimental Technology Co., Ltd.); ammonium acetate (chromatographic grade, Shanghai Anpu Experimental Technology Co., Ltd.); acetonitrile (chromatographic grade, Merck AG, Germany); isopropanol (chromatographic grade, Merck AG, Germany); purified water (self-made using a Millipore pure water system).

[0061] 2. Instruments

[0062] An Agilent 126 liquid chromatograph (Agilent Technologies, USA) equipped with a UV detector; a CAPCELL PAK C8 column (150×0.46mm, 5μm) (Shiseido, Japan).

[0063] Example 1

[0064] 1. Sample pretreatment

[0065] Weigh 150 mg of a hexane solution of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate into a 50 mL volumetric flask pre-filled with 5 mL of DMAC. Dissolve the solution in dichloromethane, bring the volume to a final volume, and mix well to obtain test solution 1.

[0066] Transfer 5 mL of DMAC to a 50 mL volumetric flask, add dichloromethane to make up to volume, mix well, and obtain a blank solution.

[0067] Weigh N,N,-Di(hexadecyl)aniline standard as the first standard, and weigh 30 mg, 40 mg and 50 mg respectively into three 50 mL volumetric flasks pre-filled with 5 mL DMAC. Dissolve, dilute to volume and mix with dichloromethane to obtain three first standard solutions of different concentrations.

[0068] Weigh out N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate standard as the second standard, and weigh out 50 mg, 60 mg and 70 mg respectively into three 50 mL volumetric flasks pre-filled with 5 mL DMAC. Dissolve, dilute to volume and mix with dichloromethane to obtain three second standard solutions of different concentrations.

[0069] 2. Measurement

[0070] The test solution 1, blank solution, first standard solution, and second standard solution prepared in step 1 above were analyzed by HPLC. Qualitative analysis was performed by comparing retention times. The elution position of the cation of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate in test solution 1 was determined by the retention time of the first standard in the first standard solution. The elution position of the anion of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate in test solution 1 was determined by the retention time of the second standard in the second standard solution. The specific HPLC chromatograms of the determination results are shown below. Figure 1 , 2 3. By Figure 1 , 2 Comparison of 1 and 3 shows that the separation effect of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate between anions and cations is obvious in test solution 1, the first standard solution and the second standard solution.

[0071] Quantification was then performed using the external standard method. This involved conducting HPLC analysis on a series of first and second standard solutions of different concentrations to obtain the linear relationships between the peak area and corresponding concentration of the first standard in the first standard solution and the peak area and corresponding concentration of the second standard in the second standard solution. Linear fitting was then performed to calculate the regression equations for the standard working curves of the first and second standards. The standard working curves of the first and second standards were plotted with peak area on the ordinate (Y-axis) and their corresponding concentrations on the abscissa (X-axis). Specific results are shown in [link to results]. Figure 4 , 5 Table 2. From Figure 4 , 5 As shown in Table 2, the standard working curves of the first and second standards exhibit good linearity and high accuracy within their respective injection concentration ranges.

[0072] Table 2 Linear Relationships

[0073]

[0074] Then, the test solution 1 was subjected to HPLC detection. The chromatographic peak area of ​​the cation of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate was substituted into the regression equation of the standard working curve of the first standard, and the chromatographic peak area of ​​the anion of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate was substituted into the regression equation of the standard working curve of the second standard. The contents of the cation and anion of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate in the test solution 1 were calculated, thereby determining the content of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate composed of cation and anion in the test solution 1. Among them, the external standard method was calculated according to formula (1).

[0075] For specific determination, the HPLC detection conditions were as follows: detector was a UV detector; column was a CAPCELLPAK C8 column (150 mm × 0.46 mm, 5 μm); column temperature was 40 ℃; injection volume was 5 μL; flow rate was 1.0 mL / min; detection wavelength was 212 nm; mobile phase was 2 mM ammonium acetate aqueous solution-acetonitrile-isopropanol, wherein phase A was 2 mM ammonium acetate aqueous solution, phase B was acetonitrile, and phase C was isopropanol; analysis time was 40 min; gradient elution was used.

[0076] The specific procedure for gradient elution is shown in Table 1:

[0077] From 0 to 10 minutes, the volume ratio of phase A: phase B: phase C is 50:50:0-0:100:0;

[0078] 10-15 min, the volume ratio of phase A: phase B: phase C is 0:100:0-0:45:55;

[0079] For 15-40 minutes, the volume ratio of phase A: phase B: phase C is 0:45:55-0:45:55.

[0080] Example 2

[0081] 1. Sample pretreatment

[0082] Weigh 100 mg of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate in hexane into a 50 mL volumetric flask pre-filled with 5 mL of DMF. Dissolve, dilute to volume, and mix well to obtain test solution 2.

[0083] Transfer 5 mL of DMF to a 50 mL volumetric flask, add n-hexane to make up to volume, mix well, and obtain a blank solution.

[0084] Weigh N,N,-Di(hexadecyl)aniline standard as the first standard, and weigh 30 mg, 40 mg and 50 mg respectively into three 50 mL volumetric flasks pre-filled with 5 mL DMF. Dissolve, dilute to volume and mix with n-hexane to obtain three first standard solutions of different concentrations.

[0085] Weigh out N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate standard as the second standard, and weigh out 50 mg, 60 mg and 70 mg respectively into three 50 mL volumetric flasks pre-filled with 5 mL of DMF. Dissolve in n-hexane, dilute to volume and mix well to obtain three second standard solutions of different concentrations.

[0086] 2. Measurement

[0087] HPLC was used to detect the contents of test solution 2, blank solution, first standard solution, and second standard solution, respectively. Qualitative analysis was performed by comparing retention times, and quantification was performed using the external standard method to determine the content of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate, composed of cations and anions, in test solution 2. The specific qualitative and quantitative procedures were the same as step 2 in Example 1.

[0088] For specific determination, the HPLC detection conditions were as follows: detector was a UV detector; column was a CAPCELLPAK C8 column (150 mm × 0.46 mm, 5 μm); column temperature was 35 ℃; injection volume was 2 μL; flow rate was 0.8 mL / min; detection wavelength was 210 nm; mobile phase was 3 mM ammonium acetate aqueous solution-acetonitrile-isopropanol, wherein phase A was 3 mM ammonium acetate aqueous solution, phase B was acetonitrile, and phase C was isopropanol; analysis time was 40 min; gradient elution was used.

[0089] The specific procedure for gradient elution is the same as step 2 in Example 1.

[0090] Example 3

[0091] 1. Sample pretreatment

[0092] Weigh 200 mg of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate in hexane into a 50 mL volumetric flask pre-filled with 5 mL of DMSO. Add n-heptane to dissolve, dilute to volume, and mix well to obtain test solution 3.

[0093] Transfer 5 mL of DMSO to a 50 mL volumetric flask, add n-heptane to make up to volume, mix well, and obtain a blank solution.

[0094] Weigh N,N,-Di(hexadecyl)aniline standard as the first standard, and weigh 30 mg, 40 mg and 50 mg respectively into three 50 mL volumetric flasks pre-filled with 5 mL DMSO. Dissolve, dilute to volume and mix with n-heptane to obtain three first standard solutions of different concentrations.

[0095] Weigh out N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate standard as the second standard, and weigh out 50 mg, 60 mg and 70 mg respectively into three 50 mL volumetric flasks that have been pre-filled with 5 mL DMSO. Dissolve in n-heptane, dilute to volume and mix well to obtain three second standard solutions of different concentrations.

[0096] 2. Measurement

[0097] HPLC was used to detect the contents of the test solution 3, blank solution, first standard solution, and second standard solution, respectively. Qualitative analysis was performed by comparing retention times, and quantitative analysis was performed using the external standard method to determine the content of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate, composed of cations and anions, in the test solution 3. The specific qualitative and quantitative procedures were the same as step 2 in Example 1.

[0098] For specific determination, the HPLC detection conditions were as follows: detector was a UV detector; column was a CAPCELLPAK C8 column (150 mm × 0.46 mm, 5 μm); column temperature was 45 ℃; injection volume was 8 μL; flow rate was 1.2 mL / min; detection wavelength was 214 nm; mobile phase was 4 mM ammonium acetate aqueous solution-acetonitrile-isopropanol, wherein phase A was 4 mM ammonium acetate aqueous solution, phase B was acetonitrile, and phase C was isopropanol; analysis time was 40 min; gradient elution was used.

[0099] The specific procedure for gradient elution is the same as step 2 in Example 1.

[0100] Example 4

[0101] Three batches of hexane solutions of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate produced at different times were taken and numbered 1#, 2#, and 3#, respectively. Blank solution, first standard solution, second standard solution, test solution 1#, test solution 2#, and test solution 3# were prepared according to step 1 in Example 1, and measured according to step 2 in Example 1. The contents of anions and cations in N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate in test solutions 1#, 2#, and 3# were calculated using formula (1). Each sample was measured in parallel 5 times, and the calculation results are shown in Table 3. As can be seen from Table 3, the RSD of the results of this method for determining the content of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate is <0.3%, indicating that the method has high precision and good reproducibility.

[0102] Table 3. Precision results of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate content in samples (n=5)

[0103]

[0104] Example 5

[0105] Take three appropriate amounts of n-hexane solution of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate (numbered 1# in Example 4), and add different masses of the first and second standards respectively to obtain three spiked samples 1#-1, 1#-2, and 1#-3. Prepare the spiked sample solutions 1#-1, 1#-2, 1#-3, blank solution, first standard solution, and second standard solution according to step 1 in Example 1, and perform the determination according to step 2 in Example 1. Calculate the content of anions and cations in N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate in the spiked sample solutions 1#-1, 1#-2, and 1#-3 respectively using formula (1). Each spiked sample was measured in triplicate, and the calculation results are shown in Table 4. As shown in Table 4, the recovery rate of the anions and cations in N,N,-bis(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate by this method is 98-102%, and the determination results are highly accurate.

[0106] Table 4. Results of the method accuracy test

[0107]

[0108] Example 6

[0109] A hexane solution of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate (sample number 2# from Example 4) was used to prepare the test solution according to step 1 in Example 1, and the determination was performed according to step 2 in Example 1. When the test solution was detected by HPLC, different proportions of mobile phase were used for isocratic elution. The results are shown in Table 5.

[0110] Table 5 Results of determination of different eluent ratios

[0111]

[0112] As shown in Table 5, considering factors such as the separation degree between anions and cations and adjacent impurity components, peak shape, and impurity elution, it is clear that the existing gradient elution conditions have shortcomings. Only when using the gradient elution with preferred conditions as described in step 2 of Example 1 of this invention can the main peak and adjacent impurities be effectively separated.

[0113] In summary, this invention provides a method for detecting the content of active ingredients in perfluoroarylborate solutions. This method achieves complete separation of N,N,-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate and related impurities. The method exhibits high precision, accurate results, simple quantification, and good repeatability. Therefore, this invention effectively overcomes the various shortcomings of existing technologies and possesses high industrial applicability.

[0114] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A method for detecting the active ingredient content of a perfluoroaryl borate salt solution, comprising: The sample of N,N,-di(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate is added to the to-be-tested solution obtained after dissolving in the first organic solvent and the second organic solvent, and detected by high performance liquid chromatography with double standard samples; the retention time of the to-be-tested solution and the first standard sample and the second standard sample is compared for qualitative analysis, and the content of N,N,-di(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate in the to-be-tested solution is determined by external standard method; The detection by high performance liquid chromatography with double standard samples comprises the following steps: 1) The double standard sample is divided into a first standard sample and a second standard sample, and the first standard sample and the second standard sample are respectively dissolved in the first organic solvent and the second organic solvent to prepare a first standard solution and a second standard solution; 2) The to-be-tested solution, the first standard solution and the second standard solution in step 1) are respectively detected by high performance liquid chromatography, the retention time is compared for qualitative analysis, the peak position of the cation of N,N,-di(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate in the to-be-tested solution is determined by the first standard solution, the peak position of the anion of N,N,-di(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate in the to-be-tested solution is determined by the second standard solution, and the content of N,N,-di(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate composed of the cation and the anion in the to-be-tested solution is determined by external standard method for quantitative analysis; In step 1), the first standard sample is N,N,-di(hexadecyl)aniline; and the second standard sample is N,N-dimethylphenylammonium tetrakis(pentafluorophenyl)borate; In step 2), the high performance liquid chromatography comprises the following detection conditions: the detector is an ultraviolet detector; the chromatographic column is a C8 chromatographic column; the detection wavelength is 205-215 nm; the mobile phase is 1-5 mM ammonium acetate aqueous solution-acetonitrile-isopropyl alcohol, wherein the A phase is 1-5 mM ammonium acetate aqueous solution, the B phase is acetonitrile, and the C phase is isopropyl alcohol; the analysis time is 40 min; and gradient elution is adopted.

2. The detection method of the content of the effective component in the perfluoroaryl borate solution according to claim 1, characterized in that, any one or more of the following conditions is adopted: The chemical structural formula of the N,N,-di(hexadecyl)aniline tetra(pentafluorophenyl)borate is shown in the following formula (1), and formula (1) is:

3. The method for detecting the content of active ingredient in a perfluoroaryl borate salt solution according to claim 1, characterized by, A1) the first organic solvent is selected from one of dimethylformamide, dimethylacetamide or dimethyl sulfoxide; A2) the second organic solvent is selected from one of dichloromethane, n-hexane or n-heptane; A3) the sample of N,N,-di(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate is a n-hexane solution containing N,N,-di(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate; A4) the ratio of the mass of the sample of N,N,-di(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate to the volume of the first organic solvent is 0.1-0.5:5, g / mL; A5) the ratio of the mass of the sample of N,N,-di(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate to the volume of the second organic solvent is 0.1-0.5:45, g / mL. Any one or more of the following conditions is adopted in step 1):

4. The method for detecting the content of active ingredient in a perfluoroaryl borate salt solution according to claim 1, characterized by, ​ B1) the first organic solvent is selected from one of dimethylformamide, dimethylacetamide or dimethyl sulfoxide; B2) the second organic solvent is selected from one of dichloromethane, n-hexane or n-heptane; B3) in the first standard solution, the ratio of the mass of the first standard added to the volume of the first organic solvent added to the volume of the second organic solvent added is 0.02-0.1:5:45, g / ml / ml; B4) in the second standard solution, the ratio of the mass of the second standard added to the volume of the first organic solvent added to the volume of the second organic solvent added is 0.02-0.1:5:45, g / ml / ml.

5. The method of claim 1, wherein the perfluoroaryl borate salt solution is characterized by a concentration of active ingredient. The specific procedure of the gradient elution is as follows: 0-10 min, the volume ratio of A phase:B phase:C phase is 50:50:0-0:100:0; 10-15 min, the volume ratio of A phase:B phase:C phase is 0:100:0-0:45:55; 15-40 min, the volume ratio of A phase:B phase:C phase is 0:45:55-0:45:

55.

6. The method of claim 1, wherein the perfluoroaryl borate salt solution is characterized by, In step 2), the high performance liquid chromatography further comprises the following detection conditions: the column temperature is 30-50℃; the injection amount is 2.0-10.0 μL; and the flow rate is 0.8-1.2 mL / min.

7. The method of claim 1, wherein the perfluoroaryl borate salt solution is characterized by a concentration of active ingredient of about 0.1 to about 10 wt%. In step 2), the external standard method is calculated according to formula (1), The formula (1) is: wi = [(Ai-b) / a] / c x 100%, wherein, wi is the cation or anion content of N,N,-di(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate in the test solution; Ai is the chromatographic peak area of the cation or anion of N,N,-di(hexadecyl)anilinium tetrakis(pentafluorophenyl)borate in the test solution; b is the intercept of the standard working curve of the first standard or the second standard; a is the slope of the standard working curve of the first standard or the second standard; and c is the sampling amount of the test solution, g.

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