CN112986421A - Method for valuing 4-bromodiphenyl ether purity standard substance - Google Patents

Method for valuing 4-bromodiphenyl ether purity standard substance Download PDF

Info

Publication number
CN112986421A
CN112986421A CN202110171861.6A CN202110171861A CN112986421A CN 112986421 A CN112986421 A CN 112986421A CN 202110171861 A CN202110171861 A CN 202110171861A CN 112986421 A CN112986421 A CN 112986421A
Authority
CN
China
Prior art keywords
standard substance
bromodiphenyl ether
purity
purity standard
bromodiphenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110171861.6A
Other languages
Chinese (zh)
Other versions
CN112986421B (en
Inventor
陈玲
周瑾艳
阮瑞雯
花秀兵
王世超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Provincial Institute Of Metrology (south China National Centre Of Metrology)
Original Assignee
Guangdong Provincial Institute Of Metrology (south China National Centre Of Metrology)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Provincial Institute Of Metrology (south China National Centre Of Metrology) filed Critical Guangdong Provincial Institute Of Metrology (south China National Centre Of Metrology)
Priority to CN202110171861.6A priority Critical patent/CN112986421B/en
Publication of CN112986421A publication Critical patent/CN112986421A/en
Application granted granted Critical
Publication of CN112986421B publication Critical patent/CN112986421B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/74—Optical detectors

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for valuing a 4-bromodiphenyl ether purity standard substance, which comprises the following steps: utilizing high performance liquid chromatography to determine the organic purity of the 4-bromodiphenyl ether purity standard substance; the organic purity standard substance of the 4-bromodiphenyl ether purity is subjected to value setting by utilizing gas chromatography; testing the moisture of the 4-bromodiphenyl ether purity standard substance by using a Karl Fischer moisture tester, testing inorganic elements contained in the 4-bromodiphenyl ether purity standard substance by using ICP/MS (inductively coupled plasma/mass spectrometry), and performing solvent residue analysis on the 4-bromodiphenyl ether purity standard substance by using gas-mass spectrometry; the 4-bromodiphenyl ether purity standard substance is subjected to value determination through a formula. The method for determining the value of the 4-bromodiphenyl ether purity standard substance provided by the invention has the advantages that organic impurities are determined by high performance liquid chromatography and gas chromatography, the water content is determined by a Karschner moisture analyzer, the content of inorganic impurities is determined by ICP/MS, solvent residue analysis is carried out, and the method for determining the value of the 4-bromodiphenyl ether purity standard substance by using a mass balance method has traceability.

Description

Method for valuing 4-bromodiphenyl ether purity standard substance
Technical Field
The invention belongs to the technical field of metering, and relates to a method for valuing an organic standard substance, in particular to a method for valuing a 4-bromodiphenyl ether standard substance.
Background
Polybrominated diphenyl ether is a recognized global organic pollutant, is restricted or prohibited from being used in the global scope, develops a polybrominated diphenyl ether standard substance, determines the purity and the content of impurities contained in the polybrominated diphenyl ether standard substance, and has important significance for detecting polybrominated diphenyl ether compounds and ensuring production safety and civil health.
In the prior art, a gas chromatography-mass spectrometry method is generally adopted for detecting polybrominated diphenyl ether, for example, HJ 909-2017 discloses a method for determining polybrominated diphenyl ether in water, and HJ 952-2018 discloses a method for determining polybrominated diphenyl ether in soil and sediments. 4-bromodiphenyl ether is taken as one of polybromodiphenyl ether, the accuracy of the quantitative determination of the purity of a standard substance is high, and the use requirement cannot be met by using the current gas chromatography-mass spectrometry.
Disclosure of Invention
The invention aims to provide a method for fixing a value of a 4-bromodiphenyl ether purity standard substance, which aims to solve the problem that a detection method in the prior art cannot meet the requirement of the fixed value.
According to one aspect of the present invention, there is provided a method for valuing a 4-bromodiphenyl ether purity standard substance, comprising the steps of:
the organic purity of the 4-bromodiphenyl ether purity standard substance is set to be P by utilizing high performance liquid chromatography1；
The organic purity of the 4-bromodiphenyl ether purity standard substance is set to be P by utilizing gas chromatography2；
Testing the moisture of the 4-bromodiphenyl ether purity standard substance by using a Karl Fischer moisture tester, testing inorganic elements contained in the 4-bromodiphenyl ether purity standard substance by using ICP/MS (inductively coupled plasma/mass spectrometry), and performing solvent residue analysis on a pure raw material used by the 4-bromodiphenyl ether purity standard substance by using gas chromatography-mass spectrometry;
the 4-bromodiphenyl ether purity standard was evaluated by the following formula:
P＝P0×(1-XW-XV-XNV)
in the formula:
p represents the purity of 4-bromodiphenyl ether standard substance, g/g;
P0representing the organic purity calculated by area normalization of chromatography, expressed as the ratio of the principal component in the material to the sum of the principal component and the total amount of structurally related impurities, g/g; i.e. P1And P2Average value of (d);
XWrepresents the moisture content, g/g;
XVrepresents the content of volatile components;
XNVrepresents the nonvolatile component content, g/g.
The method for determining the value of the 4-bromodiphenyl ether purity standard substance provided by the invention has the advantages that organic impurities are determined by high performance liquid chromatography and gas chromatography, the water content is determined by a Kaschin moisture analyzer, the content of inorganic impurities is determined by ICP/MS, solvent residue analysis is carried out, the 4-bromodiphenyl ether purity standard substance is determined by using a mass balance method, the purity standard value of the 4-bromodiphenyl ether is finally given, a quantity guarantee is provided for the accurate measurement of the 4-bromodiphenyl ether, technical reference is provided for the purity measurement of organic pollutants with similar structures, and traceability is realized.
In some embodiments, the 4-bromodiphenyl ether purity standard is 4-bromodiphenyl ether with a purity greater than 99%.
In some embodiments, prior to HPLC analysis, 50.2mg of 4-bromodiphenyl ether is accurately weighed and made up to 25mL with methanol to obtain a 2.0mg/mL solution of 4-bromodiphenyl ether in methanol.
In some embodiments, high performance liquid chromatography is used to quantify the organic purity of 4-bromodiphenyl ether purity standards using the following chromatographic conditions: a DAD detector, a C18 chromatographic column, methanol-water with the volume ratio of 90 percent to 10 percent as a mobile phase, the absorption wavelength of 230nm, the flow rate of 1.0mL/min and the column temperature of 30 ℃.
In some embodiments, the gas chromatography conditions used to quantify the organic purity of the 4-bromodiphenyl ether purity standards are as follows: the sample inlet temperature is 250 ℃, the detector temperature is 250 ℃, the constant flow is 6.5mL/min, the sample injection amount is 1 mu L, and the separation ratio is 1: 10; an HP-5 chromatographic column is adopted, the column temperature is 50 ℃, the retention time is 0.5min, the temperature is increased to 280 ℃ at the speed of 10 ℃/min, and the retention time is 20 min.
In some embodiments, the moisture content of the 4-bromodiphenyl ether purity material using a karl fischer moisture meter is measured as follows:
before measurement, firstly, a Kaschin moisture tester is used for carrying out method verification by using moisture standard substances;
0.1mL of 4-bromodiphenyl ether purity standard substance is transferred, the mass is accurately weighed, and the Kaschin moisture determination is carried out.
In some embodiments, the step of testing the inorganic elements contained in the 4-bromodiphenyl ether purity standard by ICP/MS is as follows:
measuring 0.12mL of 4-bromodiphenyl ether purity standard substance, accurately weighing the mass, adding the mass into a digestion tube, and respectively adding 5mL of nitric acid and 1mL of 30% hydrogen peroxide for digestion;
after the digestion is finished, taking out the inner tank, and removing acid until a small amount of residual liquid remains in the solution; transferring water to a volumetric flask with the constant volume of 25mL, filtering, and measuring 75 inorganic elements by adopting an ICP/MS semi-quantitative mode, wherein the single-point correction is carried out, the concentration of a correction point is 50 mug/L, and the detection limit of the method is 0.1 mug/L.
In some embodiments, when performing digestion, the digestion conditions are: (1) maintaining the temperature at 100 deg.C and pressure at 15.0atm for 2 min; (2) maintaining the temperature at 120 deg.C and pressure at 20.0atm for 4 min; (3) keeping the temperature at 150 deg.C and pressure at 25.0atm for 4 min; (4) maintaining the temperature at 180 deg.C and pressure at 30.0atm for 6 min; (5) keeping the temperature at 200 deg.C and pressure at 35.0atm for 10 min; (6) the temperature is 220 deg.C, the pressure is 40.0atm, and the temperature is kept for 10 min.
In some embodiments, the solvent residue analysis procedure for 4-bromodiphenyl ether purity standards using gas chromatography is as follows: accurately weighing 25.1mg of 4-bromodiphenyl ether, metering the volume to a 25mL volumetric flask by using normal hexane or dichloromethane, and carrying out gas chromatography-mass spectrometry analysis.
The reason is that in the processing process of the pure 4-bromodiphenyl ether raw material, the possible residual solvents include dichloromethane, tetrahydrofuran, chloroform and the like, so when the pure 4-bromodiphenyl ether raw material is subjected to solvent residue analysis, the pure 4-bromodiphenyl ether is accurately weighed, then n-hexane is used for fixing the volume, and then gas chromatography-mass spectrometry analysis is carried out to analyze other solvent residues except the n-hexane; 4-bromodiphenyl ether is accurately weighed, then dichloromethane is used for constant volume, and then gas chromatography-mass spectrometry analysis is carried out to analyze other solvent residues except dichloromethane. Thus, all solvent remaining analysis was performed.
Drawings
FIG. 1 is a high performance liquid chromatogram of 4-bromodiphenyl ether when pure methanol is used as a mobile phase;
FIG. 2 is a high performance liquid chromatogram of 4-bromodiphenyl ether when the mobile phase is methanol-water (volume ratio 90%: 10%);
FIG. 3 is a blank chromatogram for acetonitrile as the mobile phase;
FIG. 4 is a liquid chromatogram of 4-bromodiphenyl ether when the mobile phase is acetonitrile;
FIG. 5 is an enlarged view of a portion of FIG. 4;
FIG. 6 is a liquid chromatogram of 4-bromodiphenyl ether when the mobile phase is acetonitrile-water (volume ratio 90%: 10%);
FIG. 7 is an enlarged view of a portion of FIG. 6;
FIG. 8 is a blank liquid chromatogram of methanol with acetonitrile-water as the mobile phase;
FIG. 9 is a full-wavelength scanning liquid chromatogram of 4-bromodiphenyl ether;
FIG. 10 is a high performance chromatogram of 4-bromodiphenyl ether;
FIG. 11 is an enlarged view of a portion of FIG. 10;
FIG. 12 is a blank chromatogram of methanol;
FIG. 13 is a gas chromatogram of 4-bromodiphenyl ether;
FIG. 14 is a methanol gas chromatogram;
FIG. 15 is a gas chromatogram of 4-bromodiphenyl ether;
FIG. 16 is a methanol gas chromatogram.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The method for valuing the 4-bromodiphenyl ether purity standard substance comprises the following steps:
(1) accurately weighing 50.2mg of 4-bromodiphenyl ether, diluting to 25mL with methanol to obtain 2.0mg/mL of 4-bromodiphenyl ether methanol solution, and determining the organic purity of the 4-bromodiphenyl ether purity standard substance by high performance liquid chromatography;
(2) the organic purity standard substance of the 4-bromodiphenyl ether purity is subjected to value setting by utilizing gas chromatography;
(3) testing the moisture content of the 4-bromodiphenyl ether purity substance by using a Karl Fischer moisture tester;
(4) testing inorganic elements contained in the 4-bromodiphenyl ether purity standard substance by ICP/MS;
(5) and (3) carrying out solvent residue analysis on the pure raw materials for preparing the 4-bromodiphenyl ether purity standard substance by adopting gas chromatography-mass spectrometry.
The above steps will be described in detail.
Optimization and determination of high performance liquid chromatography analysis method
First, the present invention uses a C18 column (250mm 4.6mm 5 μm) to select a mobile phase.
Fig. 1 is a high performance liquid chromatogram of 4-bromodiphenyl ether when pure methanol is used as a mobile phase, fig. 2 shows a high performance liquid chromatogram of 4-bromodiphenyl ether when the mobile phase is methanol-water (volume ratio 90:10), and as can be seen from a comparison between fig. 1 and fig. 2, impurity components cannot be effectively separated when pure methanol is used as the mobile phase, and impurity components can be better separated when methanol-water (volume ratio 90:10) is used as the mobile phase.
Meanwhile, the elution effect of pure acetonitrile is compared, as shown in fig. 3 and 4, fig. 3 shows a blank chromatogram when the mobile phase is pure acetonitrile, fig. 4 and 5 show a liquid chromatogram when the mobile phase is pure acetonitrile and 4-bromodiphenyl ether, and the liquid chromatogram of 4-bromodiphenyl ether and the blank liquid chromatogram are compared, when the pure acetonitrile is used as the mobile phase, only two impurity peaks can be obtained by separation;
when the mobile phase is changed to be acetonitrile-water (volume ratio is 90:10), the liquid chromatogram of the obtained 4-bromodiphenyl ether is shown in figures 6 and 7; comparing with methanol blank (figure 8), the first two impurity components of the main component can be separated, but the separation degree is lower than that of methanol-water (volume ratio is 90:10) as a mobile phase, and the separation effect of the methanol is better than that of the acetonitrile due to the influence of interference peaks.
Therefore, methanol-water (90: 10 by volume) is finally used as the mobile phase.
Next, the fixed wavelength is determined:
the 4-bromodiphenyl ether purity standard substance is scanned at full wavelength, the scanning range is 200-400 nm, the scanning result is shown in figure 9, and the wavelength of 230nm is determined to be the maximum absorption wavelength of the 4-bromodiphenyl ether.
Thus, the final conditions of the liquid chromatography valuing method for 4-bromodiphenyl ether purity standards are shown in Table 1.
TABLE 14 chromatographic conditions for standard substance analysis experiments for purity of bromodiphenyl ether
Figure BDA0002939181770000041
The peak areas and the measured linear coefficients of 4-bromodiphenyl ether in methanol of different concentrations obtained by measuring the solutions of 4-bromodiphenyl ether in methanol of concentrations of 1mg/L, 10mg/L, 100mg/L, 1000mg/L and 2200mg/L, respectively, are shown in Table 2.
TABLE 2 Peak area and measured Linear coefficient of 4-bromodiphenyl ether in methanol of different concentrations
Figure BDA0002939181770000051
According to the conditions of the high performance liquid chromatography shown in Table 1, the impurity analysis of the obtained sample is shown in the figure. Comparing the high performance liquid chromatograms of 4-bromodiphenyl ether (fig. 10 and 11) and pure methanol (fig. 12) in methanol, it can be seen that 4-bromodiphenyl ether contains three impurities.
Finally, the high performance liquid chromatography results were analyzed:
from all the samples referred to in Table 2,11 samples were randomly sampled and prepared as a 2.0mg/mL solution of 4-bromodiphenyl ether in methanol, and the results of obtaining high performance liquid purity of the 11 samples are shown in Table 3.
TABLE 32.0 mg/mL of high Performance liquid chromatography purity results for 4-bromodiphenyl ether in methanol
Figure BDA0002939181770000052
The measured data were subjected to normal distribution test by the skewness coefficient and peak coefficient method, and the measured data are listed in table 4 in order of magnitude.
TABLE 4 high Performance liquid chromatography purity results
Figure BDA0002939181770000053
Figure BDA0002939181770000061
The skewness coefficient A and the kurtosis coefficient B are calculated as follows:
Figure BDA0002939181770000062
Figure BDA0002939181770000063
Figure BDA0002939181770000064
Figure BDA0002939181770000065
Figure BDA0002939181770000066
Figure BDA0002939181770000067
when P is 0.95 and n is 22, looking up the table D.1 to obtain A1 which is 0.71 and A is less than A1;
the critical interval is 1.82-4.16, and the value B is within the range of the critical interval, so that the data can be accepted as the critical distribution.
Examination of outliers in experimental data:
grabbs method, in a set of measured values, if the measured value xiHaving residual error
Figure BDA0002939181770000068
When v isiWhen λ (α, n) s is larger, x isiShould be rejected. In this set of data, the maximum residual is 0.0013, and λ (5%, 22) ═ 2.758, and s ═ 5.91 × 10-4，λ(α，n)s＝2.758×5.91×10-4＝0.0016＞0.0013。
Dixon (Dixon) method: arranging the measurement data from small to large:
X(1)≤X(2)≤···≤X(n-1)≤X(n)
since the number of measurements is 22, r is calculated by the following formula1And rn。
Figure BDA0002939181770000071
If r1＞rnAnd r is1＞f(α，n)Then, X is judged(1)Is an abnormal value; if rn＞r1And r isn＞f(α，n)Then, X is judged(n)Is an abnormal value; if r1And rnAll values are less than f(α，n)Value, then all data is retained.
According to experimental data, the following are calculated: r is1＝0.133，rnLooking up table to get f 0.286(α，n)＝0.468。r1And rnAll values are less than f(α，n)The value, and therefore all data, is retained.
In summary, the average value of the quantitative results of the 4-bromodiphenyl ether purity standard substance by liquid chromatography was 0.9945.
Second, optimization and determination of gas chromatography analysis method
First, the temperature-raising program was optimized, and the 4-bromodiphenyl ether purity standard substance having a concentration of 2mg/L was subjected to gas chromatography analysis under the conditions shown in table 5, to obtain a gas chromatogram shown in fig. 13.
TABLE 5 gas chromatography conditions
Figure BDA0002939181770000072
Comparing fig. 13 with the methanol blank chromatogram (fig. 14), it can be seen that there are three impurity peaks in the gas chromatographic analysis of 4-bromodiphenyl ether, and the normalized results of the baseline separation peak area of the impurity peaks can be obtained as shown in table 6, which is consistent with the results of the liquid chromatographic analysis.
TABLE 6 area normalization results
Serial number Retention time (min) Peak area (pAs) Percentage of Peak area (%)
1 8.633 73.7 0.164
2 11.663 170.7 0.382
3 12.151 44456 99.392
4 15.065 27.6 0.062
Changing the temperature raising program to 60 ℃ as the initial temperature, keeping for 0.5min, raising the temperature to 100 ℃ at 5 ℃/min, raising the temperature to 250 ℃ at 10 ℃/min, keeping for 6.5min, and keeping for 30min, wherein under the conditions, the gas chromatogram of the obtained 4-bromodiphenyl ether and the gas chromatogram of the methanol are respectively shown in fig. 15 and fig. 16, and the peak area normalization results are shown in table 7.
TABLE 74 normalized measurement of Bromoiodiphenyl ether GC Peak area
Serial number Retention time Peak area Percent (%)
1 11.044 53.7 0.169
2 14.529 121.6 0.382
3 15.016 31630.5 99.389
4 18.048 19.1 0.060
From the analysis results, it can be seen that the measurements obtained for both temperature-raising procedures are consistent.
Next, the purity analysis results of 4-bromodiphenyl ether under the conditions of changing the injection port temperature to 250 ℃, 260 ℃, 270 ℃ and 280 ℃ are shown in Table 8.
TABLE 8 influence of injection port temperature on the results of purity analysis
Temperature at sample inlet 250℃ 260℃ 270℃ 280℃
Purity of 4-bromodiphenyl ether 0.99373 0.99326 0.99368 0.99412
As can be seen from the data in the table, the inlet temperature had no significant effect on the purity analysis in the range of 250 ℃ and 280 ℃, so the inlet temperature was still kept at 250 ℃.
Thus, the gas chromatography analysis conditions determined are seen in table 9.
TABLE 9 gas chromatography conditions
Figure BDA0002939181770000081
Under the conditions, solutions of 4-bromodiphenyl ether in methanol at concentrations of 1mg/L, 10mg/L, 100mg/L, 1000mg/L, and 2200mg/L were measured, respectively, and the gas chromatogram peak areas and the measured linear coefficients of 4-bromodiphenyl ether in methanol at different concentrations were obtained as shown in Table 10.
TABLE 10 gas chromatogram peak areas and measured linear coefficients for 4-bromodiphenyl ether in methanol of different concentrations
Figure BDA0002939181770000082
Finally, the results of the gas chromatography were analyzed:
11 samples were randomly extracted from the total samples referred to in Table 10 to prepare a 2.0mg/mL solution of 4-bromodiphenyl ether in methanol, and these 11 samples were subjected to gas chromatography purity analysis, the purity analysis results of which are shown in Table 11.
TABLE 114-gas chromatography purity analysis of bromodiphenyl ether
Figure BDA0002939181770000091
Comparing the gas chromatogram of 4-bromodiphenyl ether with methanol in methanol (fig. 13 and 14, or fig. 15 and 16), it can be seen that 4-bromodiphenyl ether contains three impurities, which is substantially consistent with the analysis result of liquid chromatography. Therefore, the initial characterization of impurities is carried out by adopting gas chromatography-mass spectrometry, and the spectral library search of the impurities is carried out, and the impurities are homologs of polybrominated diphenyl ethers.
The data measured in Table 11 were subjected to normal distribution test using the skewness factor and the peak-to-average power factor, and the data are shown in Table 12 in order of magnitude.
TABLE 124-Bromoiodiphenyl ether gas chromatography purity results
Figure BDA0002939181770000092
Figure BDA0002939181770000101
The skewness coefficient A and the kurtosis coefficient B are calculated as follows:
Figure BDA0002939181770000102
Figure BDA0002939181770000103
Figure BDA0002939181770000104
Figure BDA0002939181770000105
Figure BDA0002939181770000106
when P is 0.95 and n is 22, looking up the table D.1 to obtain A1 which is 0.71 and A is less than A1;
the critical interval is 1.82-4.16, and the value B is within the range of the critical interval, so that the data can be accepted as the critical distribution.
Examination of outliers in experimental data:
grabbs method, in a set of measured values, if the measured value xiHaving residual error
Figure BDA0002939181770000108
When v isiWhen λ (α, n) s is larger, x isiShould be rejected. In this set of data, the maximum residual is 0.0010, and λ (5%, 22) ═ 2.758, and s ═ 4.39 × 10-4，λ(α，n)s＝2.758×4.39×10-4＝0.0011＞0.0010。
Dixon (Dixon) method: arranging the measurement data from small to large:
X(1)≤X(2)≤···≤X(n-1)≤X(n)
since the number of measurements is 22, r is calculated by the following formula1And rn。
Figure BDA0002939181770000107
If r1＞rnAnd r is1＞f(α，n)Then, X is judged(1)Is an abnormal value; if rn＞r1And r isn＞f(α，n)Then, X is judged(n)Is an abnormal value; if r1And rnAll values are less than f(α，n)Value, then all data is retained.
According to experimental data, the following are calculated: r is1＝0.274，rnLooking up table to get f 0.267(α，n)＝0.468。r1And rnAll values are less than f(α，n)The value, and therefore all data, is retained.
In summary, the quantitative results of 4-bromodiphenyl ether purity standard substance using gas chromatography were averaged to obtain 0.9931.
The results of the equal accuracy tests of the gas chromatography and the liquid chromatography are shown in Table 13.
TABLE 13 accuracy test of gas chromatography and liquid chromatography
N HPLC GC
1 0.9941 0.9935
2 0.9936 0.9933
3 0.9952 0.9928
4 0.9941 0.9924
5 0.9954 0.9930
6 0.9944 0.9930
7 0.9946 0.9935
8 0.9946 0.9934
9 0.9947 0.9931
10 0.9944 0.9930
11 0.9948 0.9936
s 0.000508 0.000359
Figure BDA0002939181770000111
The Critical Table of the Charcot Kolon test, C < C (0.05,2,11), indicates that the two sets of data are of equal precision, and therefore, the average value of the purities of the gas chromatography and the liquid chromatography is taken as the organic purity result of the 4-bromodiphenyl ether.
Figure BDA0002939181770000112
Third, moisture test
The moisture test of the 4-bromodiphenyl ether purity standard substance adopts a Karl Fischer moisture tester for testing, the model number of the tester is C20, and the polarization current is 0-24 muA.
Before testing, the Karl-Lou moisture tester was used to perform the method verification using the moisture standard substance, and the results of the measurement of the 0.1% pure water standard substance are shown in Table 14.
TABLE 140.1% pure Water Standard substance measurement results
1 2 3 4 5 6 Mean value of Error in indicating value RSD
0.1023 0.1029 0.1042 0.1037 0.1054 0.1039 0.1037 +0.4％ 1.0％
The drift is less than 18 mug/min.
During measurement, the injector is placed into a balance tray and returns to zero; 0.1mL of 4-bromodiphenyl ether sample is removed, and the sample mass is accurately weighed. The Karl moisture determination was performed and the average of the 6 sample measurements was taken as the final test result.
TABLE 15 sample moisture measurements
Sample (I) 1 2 3 4 5 6 Mean value of s
Sample Mass (g) 0.1423 0.1467 0.1419 0.1456 0.1439 0.1476 -- --
Measurement results (%) 0.046 0.053 0.042 0.048 0.052 0.049 0.049 3.69
The average value of 6 4-bromodiphenyl ether samples is taken as the final moisture content, and the moisture content of the 4-bromodiphenyl ether is 0.049%.
Test of inorganic elements
The inorganic element of the 4-bromodiphenyl ether purity standard substance passes ICP/MS test, and the specific operation steps are as follows:
measuring 0.12mL of 4-bromodiphenyl ether, accurately weighing the mass, adding the weighed mass into a digestion tube, respectively adding 5mL of nitric acid and 1mL of 30% hydrogen peroxide, and digesting according to a set program, wherein the digestion program is shown in Table 16.
TABLE 16 digestion program
Step (ii) of Temperature (. degree.C.) Pressure (atm) Time (min)
1 100 15.0 2
2 120 20.0 4
3 150 25.0 4
4 180 30 6
5 200 35 10
6 220 40 10
After the digestion is finished, the inner tank is taken out, and acid is removed until a small amount of residual liquid is left in the solution. Transferring water to a volumetric flask with the constant volume of 25mL, filtering, measuring 75 inorganic elements by ICP/MS (inductively coupled plasma/mass spectrometry) in a semi-quantitative mode, and correcting single points to obtain the concentration of 50 mug/L at the correction point. The detection limit of the method is 0.1 mug/L, and the content of the elements more than 0.1 mug/L is shown in Table 17.
TABLE 174 inorganic elements in bromodiphenyl ether
Element(s) Na Mg S CL K Ca Fe
blk 14.9 0.8 15.7 5.1 1.5 8.4 2.2
Concentration of solution (ug/L) 16.02 0.37 41.23 16.52 3.78 0.54 1.21
The concentration of the external standard curve of the common elements is prepared according to the content of the common elements in the digestion solution, which is shown in a table 18.
TABLE 18 concentration of external standard curve of common elements
Element(s) Na Mg S CL K Ca Fe
Std1 1.0 0.1 1.0 1.0 1.0 0.1 0.1
Std2 5.0 0.5 5.0 5.0 10.0 1.0 0.5
Std3 10.0 1.0 10.0 10.0 100.0 10.0 1.0
Std4 40.0 5.0 40.0 40.0 300.0 50.0 5.0
Std5 80.0 10.0 80.0 80.0 600.0 100.0 10.0
Coefficient of linearity 0.9997 0.9992 0.9991 0.9993 0.9994 0.9995 0.9997
Three bottles of samples were randomly sampled, each bottle was measured to 0.12mL, the mass was accurately weighed, and ICP/MS quantitative analysis was performed after digestion, with the results shown in Table 19
TABLE 19 measurement of inorganic elements
Figure BDA0002939181770000131
Taking the average value of the three measured values as the content of inorganic element impurities: 9.45X 10-6。
Fifth, solvent residue test
In the processing process of the pure 4-bromodiphenyl ether raw material, dichloromethane, tetrahydrofuran, chloroform and the like are possible residual solvents, 25.1mg of 4-bromodiphenyl ether is accurately weighed to remove dichloromethane solvent residues, n-hexane is used for fixing the volume to a 25mL volumetric flask, and gas chromatography-mass spectrometry analysis is carried out. From the analysis of the results, no solvent other than n-hexane was detected.
Meanwhile, in order to eliminate solvent residues of n-hexane, 4-bromodiphenyl ether solution in dichloromethane with the same concentration is prepared at the same time, and gas chromatography-mass spectrometry analysis is carried out. From the analysis of the results, no solvent other than methylene chloride was detected.
Therefore, the 4-bromodiphenyl ether purity standard substance has no solvent residue.
Purity of hexa, 4-bromodiphenyl ether
And finally, based on a mass balance method with unknown all impurities, calculating the fixed value of the 4-bromodiphenyl ether purity standard substance according to the following formula:
P＝P0×(1-XW-XV-XNV)
in the formula: p represents the purity of 4-bromodiphenyl ether standard substance, g/g; p0Representing the organic purity calculated by area normalization of chromatography, expressed as the ratio of the principal component in the material to the sum of the principal component and the total amount of structurally related impurities, g/g; i.e. P1And P2Average value of (d); xWRepresents the moisture content, g/g; xVRepresents the content of volatile components; xNVRepresents the nonvolatile component content, g/g.
For the purposes of this example, the 4-bromodiphenyl ether purity standard is rated as result PMComprises the following steps:
PM＝(1-Pwater (W)-PInorganic substance)×PChromatography
＝(1-4.9×10-4-9.45×10-6)×0.9938
＝0.9932
Therefore, the 4-bromodiphenyl ether purity standard substance of this example was rated as 0.9932, giving a standard value of purity of 4-bromodiphenyl ether.

Claims (10)

  1. The method for determining the value of the 1.4-bromodiphenyl ether purity standard substance is characterized by comprising the following steps:
    the organic purity of the 4-bromodiphenyl ether purity standard substance is set to be P by utilizing high performance liquid chromatography1；
    The organic purity of the 4-bromodiphenyl ether purity standard substance is set to be P by utilizing gas chromatography2；
    Testing the moisture of the 4-bromodiphenyl ether purity standard substance by using a Karl Fischer moisture tester, testing inorganic elements contained in the 4-bromodiphenyl ether purity standard substance by using ICP/MS (inductively coupled plasma/mass spectrometry), and performing solvent residue analysis on the 4-bromodiphenyl ether purity standard substance by using gas-mass spectrometry;
    the 4-bromodiphenyl ether purity standard was evaluated by the following formula:
    P＝P0×(1-XW-XV-XNV)
    in the formula: p is 4-bromoPurity standard substance purity of diphenyl ether, g/g; p0The organic purity is calculated by an area normalization method of a chromatogram and is expressed by a ratio of a main component in a substance to the sum of the main component and the total amount of structurally related impurities, g/g; i.e. P1And P2Average value of (d); xWIs the water content, g/g; xVIs the content of volatile components; xNVIs the nonvolatile component content, g/g.
  2. 2. The method for valuing the 4-bromodiphenyl ether purity standard substance according to claim 1, wherein the 4-bromodiphenyl ether purity standard substance selects 4-bromodiphenyl ether with purity of more than 99% as the purity standard substance.
  3. 3. The method for valuing the 4-bromodiphenyl ether purity standard substance according to claim 1 or 2, wherein 50.2mg of 4-bromodiphenyl ether is accurately weighed before performing high performance liquid chromatography, and the volume is adjusted to 25mL by using methanol to prepare a methanol solution of 4-bromodiphenyl ether with the concentration of 2.0 mg/mL.
  4. 4. The method for valuing the standard substance of 4-bromodiphenyl ether purity according to claim 3, wherein the high performance liquid chromatography is used for valuing the organic purity of the standard substance of 4-bromodiphenyl ether purity, and the adopted chromatographic conditions are as follows: DAD detector, C18 chromatography column, at a volume ratio of 90%: 10% methanol-water as mobile phase, absorption wavelength 230nm, flow rate 1.0mL/min, column temperature 30 ℃.
  5. 5. The method for valuing the 4-bromodiphenyl ether purity standard substance according to claim 1 or 2, wherein the gas chromatography conditions used for valuing the organic purity of the 4-bromodiphenyl ether purity standard substance are as follows: the temperature of a sample inlet (250-; an HP-5 chromatographic column is adopted, the initial temperature is (50-60) DEG C, the retention time is 0.5min, the temperature is increased to (250-280) DEG C at the speed of 10 ℃/min, and the retention time is 20 min.
  6. 6. The method for valuing the 4-bromodiphenyl ether purity standard substance according to claim 1 or 2, wherein the gas chromatography conditions used for valuing the organic purity of the 4-bromodiphenyl ether purity standard substance are as follows: the temperature of a sample inlet (250-; an HP-5 chromatographic column is adopted, the initial temperature is (50-60) DEG C, the retention time is 0.5min, the temperature is increased to 100 ℃ at the speed of 5 ℃/min, then the temperature is increased to (250-280) DEG C at the speed of 10 ℃/min, and the retention time is 6.5 min.
  7. 7. The method for valuing the 4-bromodiphenyl ether purity standard substance according to claim 1 or 2, wherein the step of testing the moisture content of the 4-bromodiphenyl ether purity standard substance by using a Karl Fischer moisture tester comprises the following steps:
    before measurement, firstly, a Kaschin moisture tester is used for carrying out method verification by using moisture standard substances;
    0.1mL of 4-bromodiphenyl ether purity standard substance is transferred, the mass is accurately weighed, and the Kaschin moisture determination is carried out.
  8. 8. The method for valuing a 4-bromodiphenyl ether purity standard substance according to claim 1 or 2, wherein the step of testing inorganic elements contained in the 4-bromodiphenyl ether purity standard substance by ICP/MS is as follows:
    measuring 0.12mL of 4-bromodiphenyl ether purity standard substance, accurately weighing the mass, adding the mass into a digestion tube, and respectively adding 5mL of nitric acid and 1mL of 30% hydrogen peroxide for digestion;
    after the digestion is finished, taking out the inner tank, and removing acid until a small amount of residual liquid remains in the solution; transferring water to a volumetric flask with the constant volume of 25mL, filtering, and measuring 75 inorganic elements by adopting an ICP/MS semi-quantitative mode, wherein the single-point correction is carried out, the concentration of a correction point is 50 mug/L, and the detection limit of the method is 0.1 mug/L.
  9. 9. The method for valuing the 4-bromodiphenyl ether purity standard substance according to claim 6, wherein digestion is carried out under the following digestion conditions: (1) maintaining the temperature at 100 deg.C and pressure at 15.0atm for 2 min; (2) maintaining the temperature at 120 deg.C and pressure at 20.0atm for 4 min; (3) keeping the temperature at 150 deg.C and pressure at 25.0atm for 4 min; (4) maintaining the temperature at 180 deg.C and pressure at 30.0atm for 6 min; (5) keeping the temperature at 200 deg.C and pressure at 35.0atm for 10 min; (6) the temperature is 220 deg.C, the pressure is 40.0atm, and the temperature is kept for 10 min.
  10. 10. The method for valuing the 4-bromodiphenyl ether purity standard substance according to claim 1 or 2, wherein the step of performing solvent residue analysis on the 4-bromodiphenyl ether purity standard substance by using gas chromatography-mass spectrometry comprises the following steps: accurately weighing 25.1mg of 4-bromodiphenyl ether, metering the volume to a 25mL volumetric flask by using normal hexane or dichloromethane, and carrying out gas chromatography-mass spectrometry analysis.
CN202110171861.6A 2021-02-08 2021-02-08 Method for valuing 4-bromodiphenyl ether purity standard substance Active CN112986421B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110171861.6A CN112986421B (en) 2021-02-08 2021-02-08 Method for valuing 4-bromodiphenyl ether purity standard substance

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110171861.6A CN112986421B (en) 2021-02-08 2021-02-08 Method for valuing 4-bromodiphenyl ether purity standard substance

Publications (2)

Publication Number Publication Date
CN112986421A true CN112986421A (en) 2021-06-18
CN112986421B CN112986421B (en) 2021-11-16

Family

ID=76347457

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110171861.6A Active CN112986421B (en) 2021-02-08 2021-02-08 Method for valuing 4-bromodiphenyl ether purity standard substance

Country Status (1)

Country Link
CN (1) CN112986421B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105467054A (en) * 2015-12-08 2016-04-06 国家纺织服装产品质量监督检验中心（浙江桐乡） Method for measuring PBB (polybrominated biphenyl) and PBDE (polybrominated diphenyl ether) fire retardants in textile with ultra-high performance liquid chromatography
CN111175418A (en) * 2020-02-25 2020-05-19 江西省科学院 Method for simultaneously detecting multiple trace amount persistent halogenated organic pollutants in insect body

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105467054A (en) * 2015-12-08 2016-04-06 国家纺织服装产品质量监督检验中心（浙江桐乡） Method for measuring PBB (polybrominated biphenyl) and PBDE (polybrominated diphenyl ether) fire retardants in textile with ultra-high performance liquid chromatography
CN111175418A (en) * 2020-02-25 2020-05-19 江西省科学院 Method for simultaneously detecting multiple trace amount persistent halogenated organic pollutants in insect body

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
国家市场监督管理总局: "纯度标准物质定值计量技术规范-有机物纯度标准物质", 《中华人民共和国国家计量技术规范》 *
李锦花等: "加速溶剂萃取-高效液相色谱法检测瓦楞纸箱(板)中的多溴二苯醚", 《食品安全质量检测学报》 *
环境保护部: "HJ909-2017水质多溴二苯醚的测定气相色谱质谱法", 《中华人民共和国国家环境保护标准》 *

Also Published As

Publication number Publication date
CN112986421B (en) 2021-11-16

Similar Documents

Publication Publication Date Title
CN110031573B (en) Method for measuring vitamin D content by two-dimensional column switching high performance liquid chromatography
CN110808203B (en) Device and method for quickly and accurately detecting impurities in high-purity hydrogen for hydrogen fuel cell
CN110031557B (en) Method for detecting 5-isoquinoline methyl sulfonate and 5-isoquinoline ethyl sulfonate in fasudil hydrochloride
CN110988104A (en) Hydrogen isotope gas quadrupole mass spectrometry based on double correction
CN110702832A (en) Application of high-content 4-hydroxyquinoline as characteristic marker of jujube honey
CN114994212A (en) High performance liquid chromatography detection method for hydroxylamine residue in medicine
CN112986421B (en) Method for valuing 4-bromodiphenyl ether purity standard substance
CN111272941B (en) Ultra-high performance liquid chromatography determination method for bear gall powder in phlegm-heat clear injection
CN114216988B (en) Method for detecting related substances of 4- (methylamino) -1- (3-pyridyl) -1-butanone hydrochloride
CN114646690B (en) Detection method for chemical components in immature bitter orange, longstamen onion bulb and cassia twig decoction and fingerprint establishment method
CN115047099A (en) Method for rapidly determining content of total terpene lactones in elution process of ginkgo leaf extract
CN113009011A (en) 4,4&#39; -dibromodiphenyl ether purity standard substance and preparation method thereof
CN114755326B (en) Detection method of difenoconazole in hydroxypropyl methylcellulose
CN112710762A (en) Method for measuring residual quantity of dimethyl sulfate
CN113109460A (en) Method for analyzing high-boiling-point solvent residue in OLED material
CN114646720B (en) Quality detection method for standard decoction of vinegar myrrh
CN112461957B (en) Method for detecting impurity content in ulipristal acetate intermediate II
CN111537593B (en) Method for measuring content of tetrahydropalmatine and tetrahydroberberine chiral enantiomers in corydalis extracting solution
CN117805273B (en) Quantitative detection method and application of 5 aristolochic acid substances in diarrhea-relieving capsule
Onal et al. Development and validation of a stability-indicating ultra-fast liquid chromatographic analysis for the simultaneous determination of fenticonazole and its related substances in pharmaceutical formulations
CN106501417A (en) The quick method for determining protodioscin content in Rhizoma Dioscoreae Zingiberensiss
CN115236258B (en) Method for simultaneously determining glycine anhydride and DL-methionine sulfoxide in sample
CN116840375A (en) Analysis method for thiourea and guanylthiourea content in famotidine
CN107677742B (en) Quantitative detection method for residual hydroxyethyl acrylate in polymer synthesis process
CN106483224B (en) Method for rapidly determining content of methylprotodioscin in dioscorea zingiberensis

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant