CN112557531B - Method for detecting residual solvent in vinyl sulfate by headspace gas chromatography - Google Patents
Method for detecting residual solvent in vinyl sulfate by headspace gas chromatography Download PDFInfo
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Abstract
The invention provides a method for detecting residual solvent in vinyl sulfate by headspace gas chromatography, which comprises the following steps: and (3) adding a vinyl sulfate sample into a sample solution obtained after the dissolution of the organic solvent, detecting by using a headspace-gas chromatography-flame ionization detector (HS-GC-FID), and determining the content of residual methylene dichloride, cyclohexane, n-heptane and o-xylene in the sample solution. The method for detecting the residual solvent in the vinyl sulfate by headspace gas chromatography provided by the invention can realize complete separation of the relevant residual solvent in the vinyl sulfate, has good precision and accuracy, and accurate result, and has important significance for monitoring the quality of the vinyl sulfate.
Description
Technical Field
The invention belongs to the technical field of component analysis, relates to a method for detecting residual solvents in vinyl sulfate by headspace gas chromatography, and in particular relates to a method for detecting residues of methylene dichloride, cyclohexane, n-heptane and o-xylene in vinyl sulfate by using a headspace-gas chromatography-flame ionization detector method (HS-GC-FID).
Background
Vinyl sulfate, chemical name 1,3, 2-dioxazothiophene-2, 2-dioxide, english name ethyl sulfate, is an additive of lithium ion battery electrolyte. In practice, it is necessary to control the quality of the solvent residue in the vinyl sulfate. The existing solvent residue detection method comprises a gas chromatography external standard method or an internal standard method, a drying weightlessness method and the like. The gas chromatography is commonly used in solvent residue detection, but the sensitivity of gas direct sample injection cannot meet the detection requirement of low-content solvent residue, the detection result is poor in accuracy, and the sample is easy to absorb water and hydrolyze in humid air and shows strong acidity, so that certain damage is caused to a chromatographic column. The dry weight loss method cannot effectively reflect the solvent attribute and has poor accuracy. At the same time, the special nature of vinyl sulfate can chemically react with many reagents, such as: common solvents for the headspace such as N, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide. Therefore, there is a need for improvements in existing methods for detecting residual solvents in vinyl sulfate.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a method for detecting residual solvents in vinyl sulfate by headspace gas chromatography, which can precisely and accurately detect the residual content of various solvents in vinyl sulfate.
To achieve the above and other related objects, the present invention provides a method for detecting residual solvent in vinyl sulfate by headspace gas chromatography, comprising: and (3) adding a vinyl sulfate sample into a sample solution obtained after the dissolution of the organic solvent, detecting by using a headspace-gas chromatography-flame ionization detector (HS-GC-FID), and determining the content of residual methylene dichloride, cyclohexane, n-heptane and o-xylene in the sample solution.
Preferably, the organic solvent is selected from one of chlorobenzene, toluene, diethyl carbonate and ethylmethyl carbonate.
Preferably, the organic solvent is chlorobenzene.
Preferably, the ratio of the added mass of the vinyl sulfate sample to the added volume of the organic solvent is 0.1-1.0:1-5 g/mL.
Preferably, the CAS number of the dichloromethane is 75-09-2; the CAS number of the cyclohexane is 110-82-7; the CAS number of the n-heptane is 142-82-5; the CAS number of the o-xylene is 95-47-6.
Preferably, the detection by using a headspace-gas chromatography-flame ionization detector method comprises the following steps:
1) Preparing a standard solution: taking standard substances of dichloromethane, cyclohexane, n-heptane and o-xylene, adding an organic solvent for dissolution, and then fixing the volume to prepare a standard solution;
2) Sample detection: and respectively detecting the standard solution and the sample solution by adopting a headspace-gas chromatography-flame ionization detector method, comparing the retention time for qualitative determination, and quantifying by adopting an external standard method to determine the contents of dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution.
Preferably, in the step 1), the ratio of the added mass of the standard substances of the methylene dichloride, the cyclohexane, the n-heptane and the o-xylene to the added volume of the organic solvent is 0.1-0.5:0.1-0.5:0.1-0.5:0.1-0.5:5000, g/g/g/g/mL.
Preferably, in step 1), the organic solvent is selected from one of chlorobenzene, toluene, diethyl carbonate, and ethylmethyl carbonate. More preferably, the organic solvent is chlorobenzene.
Preferably, in the step 1), the concentration of the dichloromethane in the standard solution is 0.02-0.1mg/mL, the concentration of the cyclohexane is 0.02-0.1mg/mL, the concentration of the n-heptane is 0.02-0.1mg/mL, and the concentration of the o-xylene is 0.02-0.1mg/mL.
Preferably, in step 2), the detection conditions of the headspace are: the temperature of the head space furnace is 90-110 ℃; the balance time of the headspace furnace is 30-45min.
More preferably, the detection conditions of the headspace are: the temperature of the head space furnace is 100 ℃; the balance time of the headspace furnace is 30min.
Preferably, in step 2), the temperature-increasing program used in the gas chromatography-flame ionization detector method is: the initial temperature is 40-70deg.C for 1-3min, and the temperature is raised to 240 deg.C at a rate of 5-15deg.C/min for 5-10min.
More preferably, the temperature increase program is: the initial temperature was maintained at 50deg.C for 2min, and at a rate of 10deg.C/min, the temperature was raised to 240deg.C for 5min.
Preferably, in step 2), the detection conditions of the gas chromatography-flame ionization detector method are:
the chromatographic column is DB-624 column (20-60 m×0.18-0.45mm×1.0-2.55 μm, column length×inner diameter×stationary phase film thickness), and the filler is chemically bonded 6% cyanopropylbenzene+94% methylpolysiloxane; the detector is a flame ionization detector (hydrogen flame detector, FID), and the temperature of the detector is 250-300 ℃; the temperature of the sample inlet is 250-300 ℃; the sample injection amount is 1.0-3.0mL; the carrier gas is high-purity helium, and the purity of the carrier gas is more than or equal to 99.999%; the flow rate of the carrier gas is 1.5-4.0mL/min; the sample injection mode is split sample injection, and the split ratio is 5-15:1.
More preferably, the detection conditions of the gas chromatography-flame ionization detector method are:
the chromatographic column is DB-624 column (30 m×0.32mm×1.8 μm, column length×inner diameter×stationary phase film thickness), and the filler is chemically bonded 6% cyanopropylbenzene+94% methylpolysiloxane; the detector is a flame ionization detector (hydrogen flame detector, FID), and the detector temperature is 260 ℃; the temperature of the sample inlet is 250 ℃; the sample injection amount is 1.0mL; the carrier gas is high-purity helium, and the purity of the carrier gas is more than or equal to 99.999%; the flow rate of the carrier gas is 2.0mL/min; the sample injection mode is split sample injection, and the split ratio is 5:1.
Preferably, in step 2), the external standard method comprises the following steps:
a) Preparing a series of standard solutions with different concentrations according to the step 1), respectively performing HS-GC-FID detection to obtain linear relations between chromatographic peak areas of dichloromethane, cyclohexane, n-heptane and o-xylene and the concentrations of the corresponding dichloromethane, cyclohexane, n-heptane and o-xylene, drawing corresponding standard working curves, and calculating to obtain regression equations of the standard working curves of the dichloromethane, cyclohexane, n-heptane and o-xylene;
b) And D, carrying out HS-GC-FID detection on the sample solution, substituting the chromatographic peak areas of the obtained dichloromethane, cyclohexane, n-heptane and o-xylene into the regression equation of the standard working curves of the corresponding dichloromethane, cyclohexane, n-heptane and o-xylene in the step A), and calculating to obtain the concentration of the dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution.
More preferably, in the standard working curve, the chromatographic peak areas of dichloromethane, cyclohexane, n-heptane and o-xylene are taken as an ordinate (Y axis), the concentrations of the dichloromethane, cyclohexane, n-heptane and o-xylene are taken as an abscissa (X axis), and a regression equation of the corresponding standard working curve is obtained, wherein y=ax+b. a is the slope of the curve and b is the intercept of the curve.
Preferably, in step 2), the content of dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution is calculated according to formula (1), so as to obtain the content of residual dichloromethane, cyclohexane, n-heptane and o-xylene in the vinyl sulfate, where formula (1) is: wi= [ (Y-b)/(a×c) Sample )]X 100%, wherein wi is the content of residual methylene chloride, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; y is the chromatographic peak area of residual methylene chloride, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; b is the working curve intercept of methylene dichloride, cyclohexane, n-heptane and o-xylene; a is the slope of a working curve of dichloromethane, cyclohexane, n-heptane and o-xylene; c (C) Sample Is the concentration of the vinyl sulfate sample, mg/mL.
As described above, the method for detecting the residual solvent in the vinyl sulfate by using the headspace gas chromatography provided by the invention adopts the gas chromatography system of the headspace heater and the hydrogen flame detector to analyze and detect the residual solvent in the vinyl sulfate, and can effectively determine the content of dichloromethane, cyclohexane, n-heptane and o-xylene remained in the vinyl sulfate. The method can realize complete separation of dichloromethane, cyclohexane, n-heptane and o-xylene in the vinyl sulfate, and has good precision and accuracy and good linear relation in the examined range. The method has accurate results, meets the detection requirement of the residual amount of the organic solvent, is suitable for detecting the residues of dichloromethane, cyclohexane, n-heptane and o-xylene in the vinyl sulfate, and has important significance for monitoring the quality of the vinyl sulfate.
Drawings
FIG. 1 shows a gas chromatogram of a standard solution measurement in the present invention, wherein a is methylene chloride, b is cyclohexane, c is n-heptane, and d is o-xylene.
FIG. 2 shows a gas chromatogram of a sample solution measurement in the present invention, wherein a is methylene chloride and b is n-heptane.
Detailed Description
The invention is further illustrated below in connection with specific examples, which are to be understood as being illustrative of the invention and not limiting the scope of the invention.
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
The reagents and instrumentation used in the following examples were as follows:
1. reagent(s)
Vinyl sulfate finished product (commercially available); dichloromethane (analytical purity, national medicine group chemical reagent Co., ltd., content. Gtoreq.99.5%); cyclohexane (analytical grade, national medicine group chemical reagent Co., ltd., content. Gtoreq.99.5%); n-heptane (analytically pure, national medicine group chemical reagent Co., ltd., content. Gtoreq.99.5%); o-xylene (analytically pure, national drug group chemical reagent Co., ltd., content > 99.5%); chlorobenzene (chromatographic purity, sigma-aldrich, content not less than 99.9%); toluene (chromatographic purity, TEDIA, content > 99.8%); diethyl carbonate (analytically pure, national medicine group chemical reagent Co., ltd., content. Gtoreq.99.5%); methyl ethyl carbonate (analytical grade, national medicine group chemical reagent Co., ltd., content: 99.5%).
2. Instrument for measuring and controlling the intensity of light
DANI 86.50 headspace injector (danny, italy); 2010plus gas chromatograph equipped with flame ionization detector (shimadzu corporation); DB-624 column (Agilent Co., USA).
The following measurement procedure was included for the content of methylene chloride, cyclohexane, n-heptane, o-xylene in vinyl sulfate.
1. Preparation of sample solutions
Taking a vinyl sulfate sample, and adding an organic solvent into the sample solution obtained after dissolving. The organic solvent is selected from one of chlorobenzene, toluene, diethyl carbonate and methyl ethyl carbonate. In the sample solution, the ratio of the added mass of the vinyl sulfate sample to the added volume of the organic solvent is 0.1-1.0:1-5 g/mL.
2. Preparation of standard solutions
Accurately weighing standard substances of dichloromethane, cyclohexane, n-heptane and o-xylene, adding an organic solvent for dissolution, and then fixing the volume to prepare a standard solution. Wherein the organic solvent is selected from one of chlorobenzene, toluene, diethyl carbonate and methyl ethyl carbonate, and the ratio of the added mass of the standard substances of dichloromethane, cyclohexane, n-heptane and o-xylene to the added volume of the organic solvent is 0.1-0.5:0.1-0.5:0.1-0.5:0.1-0.5:5000, g/g/g/g/mL. In the standard solution, the concentration of dichloromethane is 0.02-0.1mg/mL, the concentration of cyclohexane is 0.02-0.1mg/mL, the concentration of n-heptane is 0.02-0.1mg/mL, and the concentration of o-xylene is 0.02-0.1mg/mL.
3. Measurement
And respectively detecting the standard solution and the sample solution by adopting a headspace-gas chromatography-flame ionization detector method (HS-GC-FID), comparing the retention time for qualitative determination, and quantifying by adopting an external standard method to determine the contents of dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution.
Specifically, the external standard method can select a series of different concentrations of standard solution, respectively perform HS-GC-FID detection to obtain a linear relation between chromatographic peak areas of dichloromethane, cyclohexane, n-heptane and o-xylene and the concentrations of the corresponding dichloromethane, cyclohexane, n-heptane and o-xylene, draw a corresponding standard working curve, and calculate a regression equation of the standard working curve of the dichloromethane, cyclohexane, n-heptane and o-xylene. And then carrying out HS-GC-FID detection on the sample solution, substituting the chromatographic peak areas of the obtained dichloromethane, cyclohexane, n-heptane and o-xylene into a regression equation of standard working curves of the corresponding dichloromethane, cyclohexane, n-heptane and o-xylene, and calculating to obtain the concentration of the dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution.
Wherein, the detection condition of headspace is: the temperature of the head space furnace is 90-110 ℃; the balance time of the headspace furnace is 30-45min. In the gas chromatograph-flame ionization detector method, the temperature-increasing program is adopted as follows: the initial temperature is 40-70deg.C for 1-3min, and the temperature is raised to 240 deg.C at a rate of 5-15deg.C/min for 5-10min.
The detection conditions of the gas chromatography-flame ionization detector method are as follows: the chromatographic column is DB-624 column (20-60 m×0.18-0.45mm×1.0-2.55 μm, column length×inner diameter×stationary phase film thickness), and the filler is chemically bonded 6% cyanopropylbenzene+94% methylpolysiloxane; the detector is a flame ionization detector (hydrogen flame detector, FID), and the temperature of the detector is 250-300 ℃; the temperature of the sample inlet is 250-300 ℃; the sample injection amount is 1.0-3.0mL; the carrier gas is high-purity helium, and the purity of the carrier gas is more than or equal to 99.999%; the flow rate of the carrier gas is 1.5-4.0mL/min; the sample injection mode is split sample injection, and the split ratio is 5-15:1.
The contents of dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution are calculated according to a formula (1), so as to obtain the contents of the dichloromethane, cyclohexane, n-heptane and o-xylene remained in the vinyl sulfate, wherein the formula (1) is as follows: wi= [ (Y-b)/(a×c) Sample )]X 100%, wherein wi is the content of residual methylene chloride, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; y is the chromatographic peak area of residual methylene chloride, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; b is the working curve of dichloromethane, cyclohexane, n-heptane and o-xyleneIntercept; a is the slope of a working curve of dichloromethane, cyclohexane, n-heptane and o-xylene; c (C) Sample Is the concentration of the vinyl sulfate sample, mg/mL.
Example 1
1. Preparation of sample solutions
A sample of 0.5g of vinyl sulfate was weighed, and 5mL of chlorobenzene was added to dissolve the sample solution. Two replicates were prepared for each batch.
2. Preparation of standard solutions
Accurately weighing standard substances of 0.5g of dichloromethane, 0.5g of cyclohexane, 0.5g of n-heptane and 0.5g of o-xylene, adding 20mL of chlorobenzene, dissolving in a 50mL volumetric flask, then fixing the volume, uniformly mixing, precisely transferring 0.2mL, 0.5mL and 1.0mL of the solution into 3 100mL volumetric flasks, fixing the volume by using chlorobenzene, uniformly mixing to obtain 3 standard solutions, namely standard solution 1, wherein the concentration of dichloromethane is 0.02mg/mL, the concentration of cyclohexane is 0.02mg/mL, the concentration of n-heptane is 0.02mg/mL, and the concentration of o-xylene is 0.02mg/mL; standard solution 2, wherein the concentration of dichloromethane is 0.05mg/mL, the concentration of cyclohexane is 0.05mg/mL, the concentration of n-heptane is 0.05mg/mL, and the concentration of o-xylene is 0.05mg/mL; the standard solution 3 has a concentration of 0.10mg/mL of methylene chloride, a concentration of 0.10mg/mL of cyclohexane, a concentration of 0.10mg/mL of n-heptane, and a concentration of 0.10mg/mL of o-xylene.
3. Measurement
And respectively detecting the standard solution and the sample solution by adopting a headspace-gas chromatography-flame ionization detector method (HS-GC-FID), comparing the retention time for qualitative determination, and quantifying by adopting an external standard method to determine the contents of dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution. The gas chromatograms of the specific measurement results are shown in fig. 1 and 2, and as can be seen from fig. 1 and 2, the separation effect of methylene dichloride, cyclohexane, n-heptane and o-xylene in the standard solution and the sample solution is obvious.
Specifically, the external standard method is to perform HS-GC-FID detection on a series of standard solutions with different concentrations respectively to obtain linear relations between chromatographic peak areas of dichloromethane, cyclohexane, n-heptane and o-xylene and the concentrations of the corresponding dichloromethane, cyclohexane, n-heptane and o-xylene, draw corresponding standard working curves, and calculate regression equations of the standard working curves of the dichloromethane, cyclohexane, n-heptane and o-xylene. And then carrying out HS-GC-FID detection on the sample solution, substituting the chromatographic peak areas of the obtained dichloromethane, cyclohexane, n-heptane and o-xylene into a regression equation of standard working curves of the corresponding dichloromethane, cyclohexane, n-heptane and o-xylene, and calculating to obtain the concentration of the dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution.
Wherein, the detection condition of headspace is: the temperature of the head space furnace is 100 ℃; the balance time of the headspace furnace is 30min. In the gas chromatograph-flame ionization detector method, the temperature-increasing program is adopted as follows: the initial temperature was maintained at 50deg.C for 2min, and at a rate of 10deg.C/min, the temperature was raised to 240deg.C for 5min.
The detection conditions of the gas chromatography-flame ionization detector method are as follows: the chromatographic column is DB-624 column (30 m×0.32mm×1.8 μm, column length×inner diameter×stationary phase film thickness), and the filler is chemically bonded 6% cyanopropylbenzene+94% methylpolysiloxane; the detector is a flame ionization detector (hydrogen flame detector, FID), and the detector temperature is 260 ℃; the temperature of the sample inlet is 250 ℃; the sample injection amount is 1.0mL; the carrier gas is high-purity helium, and the purity of the carrier gas is more than or equal to 99.999%; the flow rate of the carrier gas is 2.0mL/min; the sample injection mode is split sample injection, and the split ratio is 5:1.
The contents of dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution are calculated according to a formula (1), so as to obtain the contents of the dichloromethane, cyclohexane, n-heptane and o-xylene remained in the vinyl sulfate, wherein the formula (1) is as follows: wi= [ (Y-b)/(a×c) Sample )]X 100%, wherein wi is the content of residual methylene chloride, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; y is the chromatographic peak area of residual methylene chloride, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; b is the working curve intercept of methylene dichloride, cyclohexane, n-heptane and o-xylene; a is the slope of a working curve of dichloromethane, cyclohexane, n-heptane and o-xylene; c (C) Sample Is the concentration of the vinyl sulfate sample, mg/mL.
Example 2
The series of standard solutions of different concentrations prepared in step 2 of example 1 were subjected to HS-GC-FID analysis with respect to the concentration of methylene chloride, cyclohexane, n-heptane, o-xylene as the ordinate (Y-axis) and the chromatographic peak areas of methylene chloride, cyclohexane, n-heptane, o-xylene as the abscissa (X-axis) to obtain regression equations of methylene chloride, cyclohexane, n-heptane, o-xylene and their correlation coefficients, as shown in table 1. As is clear from Table 1, the standard curves of methylene chloride, cyclohexane, n-heptane and o-xylene have good linear relationship, and the correlation coefficient r is more than 0.999. The matrix with the lowest concentration is matched with a standard solution for carrying out 10 times of HS-GC-FID parallel detection analysis, the concentration corresponding to the signal to noise ratio of 3 times is taken as the detection limit, the detection limit of methylene dichloride is 0.03 mug/mL, the detection limit of cyclohexane is 0.005 mug/mL, the detection limit of n-heptane is 0.01 mug/mL, and the detection limit of o-xylene is 0.05 mug/mL.
TABLE 1
Note that: y: peak area; x: concentration of
Example 3
Sample solutions were prepared according to step 1 and standard solutions were prepared according to step 2 in example 1, and were measured according to step 3 in example 1, and the residual solvent contents of methylene chloride, cyclohexane, n-heptane and o-xylene in the sample solutions were calculated by the formula (1), respectively. Each sample was assayed 5 times in parallel and the results are shown in tables 2-5. As can be seen from tables 2-5, the method determines that the RSD of methylene dichloride in vinyl sulfate is less than 5%; determining cyclohexane result RSD < 6% in vinyl sulfate; determining an n-heptane result RSD < 4% in the vinyl sulfate; the precision of the measurement result is high and the repeatability is good.
Table 2 results of precision of dichloromethane in sample solution (n=5)
Table 3 precision results of cyclohexane in sample solutions (n=5) confirmation data
Table 4 results of precision of n-heptane in sample solution (n=5) confirmation data
Table 5 results of precision of ortho-xylene in sample solutions (n=5) confirmation data
Example 4
Sample # 1 in example 3 was taken, a sample solution was prepared as in step 1 of example 1 and a standard solution was prepared as in step 2, wherein the sample was dissolved with the standard solution 2 in step 2 instead of chlorobenzene, and the determination was performed as in step 3 of example 1, and the residual solvent content in the sample solution was calculated by the formula (1). The recovery was calculated by 5 replicates and is shown in Table 6. As can be seen from Table 6, the average recovery rate of the method is 90-110%, and the method accuracy is high.
Table 6 method accuracy test results (n=5) validation data
Example 5
Sample number 1# in example 3 was taken, a sample solution was prepared according to step 1 and a standard solution was prepared according to step 2 in example 1, and when the detection was performed using HS-GC-FID, isothermal procedures with different temperature settings were used, respectively, and the results are shown in Table 7.
TABLE 7 determination of the results of the different temperature program settings
| Temperature program | Setting temperature (DEG C) | Test time/min | Peak out condition |
| Isothermal procedure | 80℃ | 50 | The chlorobenzene takes a long time to peak and has a peak difference |
| Isothermal procedure | 120℃ | 30 | Chlorobenzene and o-xylene cannot be separated |
| Isothermal procedure | 150℃ | 30 | Dichloromethane and cyclohexane cannot be separated |
| Isothermal procedure | 220 |
20 | Dichloromethane and cyclohexane, n-heptane and reagent blank peaks were not separated |
| Heating program | See example 1 | 26 | Main peak is effectively separated from all solvents to be detected |
As can be seen from Table 7, the main peak and the relevant solvent to be tested can be effectively separated when the temperature-increasing program of the preferred conditions is adopted in the invention by combining the factors such as the separation degree, peak shape and test time of the main peak and the relevant solvent to be tested.
In conclusion, the method for detecting the residual solvent in the vinyl sulfate by using the headspace gas chromatography provided by the invention can realize complete separation of the relevant residual solvent in the vinyl sulfate, has good precision and accuracy, and has an accurate result, and is of great significance to monitoring of the quality of the vinyl sulfate. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (6)
1. A method for detecting residual solvent in vinyl sulfate by headspace gas chromatography, comprising: adding a vinyl sulfate sample into a sample solution obtained after dissolving an organic solvent, detecting by adopting a headspace-gas chromatography-flame ionization detector method, and determining the content of one or more of dichloromethane, cyclohexane, n-heptane or o-xylene remained in the sample solution;
the detection method adopting a headspace-gas chromatography-flame ionization detector method comprises the following steps:
1) Preparing a standard solution: taking standard substances of dichloromethane, cyclohexane, n-heptane and o-xylene, adding an organic solvent for dissolution, and then fixing the volume to prepare a standard solution;
2) Sample detection: respectively detecting a standard solution and a sample solution by adopting a headspace-gas chromatography-flame ionization detector method, comparing the retention time for qualitative determination, and quantifying by adopting an external standard method to determine the content of the residual solvent in the sample solution;
in the step 2), the temperature-raising program adopted in the gas chromatography-flame ionization detector method is as follows: the initial temperature is kept at 50 ℃ for 2min, and the temperature is increased to 240 ℃ at the speed of 10 ℃/min and kept for 5min;
the organic solvent is selected from one of chlorobenzene, toluene, diethyl carbonate and ethylmethyl carbonate;
in the step 2), the detection conditions of the gas chromatography-flame ionization detector method are as follows: the chromatographic column is DB-624 column, the length of the column is 20-60m multiplied by the inner diameter of the column is 0.18-0.45mm multiplied by the thickness of the stationary phase film is 1.0-2.55 mu m, and the filler is chemically bonded 6% cyanopropylbenzene plus 94% methyl polysiloxane; the detector is a flame ionization detector, and the temperature of the detector is 250-300 ℃; the temperature of the sample inlet is 250-300 ℃; the sample injection amount is 1.0-3.0mL; the carrier gas is high-purity helium, and the purity of the carrier gas is more than or equal to 99.999%; the flow rate of the carrier gas is 1.5-4.0mL/min; the sample injection mode is split sample injection, and the split ratio is 5-15:1.
2. The method for detecting residual solvent in vinyl sulfate by headspace gas chromatography as recited in claim 1, wherein the ratio of the mass of the added vinyl sulfate sample to the volume of the added organic solvent is 0.1-1.0:1-5 g/mL.
3. The method for detecting residual solvent in vinyl sulfate by headspace gas chromatography according to claim 1, wherein in step 1), the ratio of the mass of the standard addition of methylene chloride, cyclohexane, n-heptane, o-xylene to the volume of the organic solvent addition is 0.1-0.5:0.1-0.5:5000, g/g/g/g/mL.
4. The method for detecting residual solvent in vinyl sulfate by headspace gas chromatography according to claim 1, wherein in step 1), the concentration of methylene chloride in the standard solution is 0.02-0.1mg/mL, the concentration of cyclohexane is 0.02-0.1mg/mL, the concentration of n-heptane is 0.02-0.1mg/mL, and the concentration of o-xylene is 0.02-0.1mg/mL.
5. The method for detecting residual solvent in vinyl sulfate by headspace gas chromatography according to claim 1, wherein in step 2), the headspace detection conditions are: the temperature of the head space furnace is 90-110 ℃; the balance time of the headspace furnace is 30-45min.
6. The method for detecting residual solvent in vinyl sulfate by headspace gas chromatography according to claim 1, wherein in step 2), the content of the residual solvent in the sample solution is calculated according to formula (1), and the content of the residual solvent in vinyl sulfate is obtained, wherein formula (1) is as follows: wi= [ (Y-b)/(a×c) Sample ）]X 100%, wherein wi is the content of residual methylene chloride, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; y is the chromatographic peak area of residual methylene chloride, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; b is the working curve intercept of methylene dichloride, cyclohexane, n-heptane or o-xylene; a is the slope of a working curve of methylene dichloride, cyclohexane, n-heptane or o-xylene; c (C) Sample Is the concentration of the vinyl sulfate sample, mg/mL.
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