CN112557531A - 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 an organic solvent for dissolving to obtain a sample solution, detecting by adopting a headspace-gas chromatography-flame ionization detector method (HS-GC-FID), and determining the content of residual dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution. The method for detecting the residual solvent in the vinyl sulfate by the headspace gas chromatography provided by the invention can realize complete separation of the related 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 solvent in vinyl sulfate by headspace gas chromatography, and particularly relates to a method for detecting residues of dichloromethane, cyclohexane, n-heptane and o-xylene in the vinyl sulfate by adopting a headspace-gas chromatography-flame ionization detector method (HS-GC-FID).
Background
The vinyl sulfate is 1,3, 2-dioxazole thiophene-2, 2-dioxide and is English name Ethylene sulfate, and is an additive of the lithium ion battery electrolyte. In practice, it is necessary to control the quality of the solvent residues in the vinyl sulfate. The existing solvent residue detection methods comprise a gas chromatography external standard or internal standard method, a drying weight loss 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 accuracy of a detection result is poor, and the sample is easy to absorb water and hydrolyze in humid air and shows strong acidity, so that a certain damage is caused to a chromatographic column. The loss-on-drying method cannot effectively react the solvent property and has poor accuracy. Meanwhile, the vinyl sulfate has special properties and can react with more reagents, such as: headspace gas-phase common solvents such as N, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide. Therefore, there is a need for an improved method for detecting residual solvent in vinyl sulfate.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for detecting residual solvents in vinyl sulfate by headspace gas chromatography, which can precisely and accurately detect the residual contents 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 an organic solvent for dissolving to obtain a sample solution, detecting by adopting a headspace-gas chromatography-flame ionization detector method (HS-GC-FID), and determining the content of residual dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution.
Preferably, the organic solvent is selected from chlorobenzene, toluene, diethyl carbonate and ethyl methyl carbonate.
Preferably, the organic solvent is chlorobenzene.
Preferably, 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.
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 is performed by a headspace-gas chromatography-flame ionization detector method, which comprises the following steps:
1) preparing a standard solution: taking a standard substance of dichloromethane, cyclohexane, n-heptane and o-xylene, adding an organic solvent for dissolving, and then fixing the volume to prepare a standard solution;
2) sample detection: respectively detecting the standard solution and the sample solution by adopting a headspace-gas chromatography-flame ionization detector method, comparing retention time for qualitative determination, and determining the contents of dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution by adopting an external standard method for quantitative determination.
Preferably, in the step 1), the ratio of the mass of the added dichloromethane, cyclohexane, n-heptane and o-xylene standard substance to the volume of the added 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 ethyl methyl 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 in the standard solution is 0.02-0.1mg/mL, the concentration of the n-heptane in the standard solution is 0.02-0.1mg/mL, and the concentration of the o-xylene in the standard solution is 0.02-0.1 mg/mL.
Preferably, in step 2), the detection conditions of the headspace are as follows: the temperature of the head space furnace is 90-110 ℃; the balance time of the top-air furnace is 30-45 min.
More preferably, the detection condition of the headspace is: the temperature of the head space furnace is 100 ℃; the balance time of the headspace furnace is 30 min.
Preferably, in the step 2), the temperature rising procedure adopted in the gas chromatography-flame ionization detector method is as follows: the initial temperature is 40-70 deg.C, and is maintained for 1-3min, and the temperature is increased to 240 deg.C at a rate of 5-15 deg.C/min, and is maintained for 5-10 min.
More preferably, the temperature raising program is: the initial temperature was 50 ℃ for 2min, and the temperature was raised to 240 ℃ at a rate of 10 ℃/min for 5 min.
Preferably, 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 (20-60m × 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-; the temperature of the sample inlet is 250-300 ℃; the sample injection amount is 1.0-3.0 mL; the carrier gas is high-purity helium, and the purity of the carrier gas is more than or equal to 99.999 percent; the flow rate of the carrier gas is 1.5-4.0 mL/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 as follows:
the chromatographic column is a DB-624 column (30m × 0.32mm × 1.8 μm, column length × inner diameter × stationary phase membrane thickness), and the packing is chemically bonded 6% cyanopropylbenzene + 94% methylpolysiloxane; the detector is a flame ionization detector (hydrogen flame detector, FID) with a detector temperature of 260 ℃; the temperature of a sample inlet is 250 ℃; the sample injection amount is 1.0 mL; the carrier gas is high-purity helium, and the purity of the carrier gas is more than or equal to 99.999 percent; the flow rate of the carrier gas is 2.0 mL/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 carrying out 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 (3) 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 curve of the corresponding dichloromethane, cyclohexane, n-heptane and o-xylene in the step A), and calculating to obtain the concentrations of the dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution.
More preferably, in the standard working curve, taking the chromatographic peak areas of dichloromethane, cyclohexane, n-heptane and o-xylene as ordinate (Y axis) and the concentrations of the corresponding dichloromethane, cyclohexane, n-heptane and o-xylene as abscissa (X axis), the 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 the step 2), the contents of dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution are calculated according to the formula (1), so as to obtain the contents of residual dichloromethane, cyclohexane, n-heptane and o-xylene in the vinyl sulfate, wherein the formula (1) is: wi ═ [ (Y-b)/(a × C)Sample (A))]X 100%, where wi is the residual content of dichloromethane, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; y is the chromatographic peak area of residual dichloromethane, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; b is the intercept of working curves of dichloromethane, cyclohexane, n-heptane and o-xylene; a is the slope of a working curve of dichloromethane, cyclohexane, n-heptane and o-xylene; cSample (A)Is the concentration of the vinyl sulfate sample, mg/mL.
As mentioned above, the method for detecting the residual solvent in the vinyl sulfate by the headspace gas chromatography provided by the invention adopts the gas chromatography system with the headspace heater and the hydrogen flame detector to analyze and detect the solvent residue of the vinyl sulfate, and can effectively measure the content of the residual dichloromethane, cyclohexane, n-heptane and o-xylene 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 an inspected range. The method has accurate result, meets the detection requirement of the residual quantity of the organic solvent, is suitable for detecting the residual quantity 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 assay in the present invention, wherein a is dichloromethane, b is cyclohexane, c is n-heptane, and d is o-xylene.
FIG. 2 shows a gas chromatogram for the measurement of a sample solution in the present invention, wherein a is dichloromethane and b is n-heptane.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The reagents and equipment used in the following examples are as follows:
1. reagent
Finished vinyl sulfate (commercially available); dichloromethane (analytically pure, chemical reagent of national drug group limited, content is more than or equal to 99.5%); cyclohexane (analytically pure, content more than or equal to 99.5% by national drug group chemical reagent limited); n-heptane (analytically pure, content not less than 99.5% by chemical reagents of national drug group, ltd.); o-xylene (analytically pure, content not less than 99.5% by chemical reagents of national drug group, ltd.); chlorobenzene (chromatographically pure, sigma-aldrich, content ≥ 99.9%); toluene (chromatographically pure, TEDIA, content. gtoreq.99.8%); diethyl carbonate (analytically pure, chemical reagent of national drug group, ltd., content is greater than or equal to 99.5%); methyl ethyl carbonate (analytically pure, content more than or equal to 99.5% by chemical reagents of national drug group, Ltd.).
2. Instrument for measuring the position of a moving object
DANI 86.50 headspace sampler (dany, italy); 2010plus gas chromatograph equipped with a flame ionization detector (shimadzu corporation, japan); DB-624 column (Agilent, USA).
The following measurement procedures were included for the contents of methylene chloride, cyclohexane, n-heptane and o-xylene in vinyl sulfate.
1. Preparation of sample solution
And (3) taking a vinyl sulfate sample, and adding an organic solvent to dissolve the vinyl sulfate sample to obtain a sample solution. The organic solvent is selected from chlorobenzene, toluene, diethyl carbonate and ethyl methyl carbonate. In the sample solution, 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.
2. Preparation of Standard solutions
Accurately weighing the standard substances of dichloromethane, cyclohexane, n-heptane and o-xylene, adding an organic solvent for dissolving, and fixing the volume to prepare a standard solution. Wherein the organic solvent is selected from chlorobenzene, toluene, diethyl carbonate and ethyl methyl carbonate, and the ratio of the mass of the added standard substances of dichloromethane, cyclohexane, n-heptane and o-xylene to the volume of the added organic solvent is 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 0.02-0.1 mg/mL.
3. Measurement of
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 determining the contents of dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution by adopting an external standard method for quantitative determination.
Specifically, the external standard method can select a series of different concentrations from the standard solution, respectively perform HS-GC-FID detection, obtain linear relations between chromatographic peak areas of dichloromethane, cyclohexane, n-heptane and o-xylene and the concentrations of corresponding dichloromethane, cyclohexane, n-heptane and o-xylene, draw corresponding standard working curves, and calculate regression equations of the standard working curves of dichloromethane, cyclohexane, n-heptane and o-xylene. And performing 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 curve of the corresponding dichloromethane, cyclohexane, n-heptane and o-xylene, and calculating to obtain the concentrations of the dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution.
Wherein, the detection conditions of the headspace are as follows: the temperature of the head space furnace is 90-110 ℃; the balance time of the top-air furnace is 30-45 min. In the gas chromatography-flame ionization detector method, the adopted temperature-raising procedure is as follows: the initial temperature is 40-70 deg.C, and is maintained for 1-3min, and the temperature is increased to 240 deg.C at a rate of 5-15 deg.C/min, and is maintained for 5-10 min.
The detection conditions of the gas chromatography-flame ionization detector method are as follows: the chromatographic column is DB-624 column (20-60m × 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-; the temperature of the sample inlet is 250-300 ℃; the sample injection amount is 1.0-3.0 mL; the carrier gas is high-purity helium, and the purity of the carrier gas is more than or equal to 99.999 percent; the flow rate of the carrier gas is 1.5-4.0 mL/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 the formula (1), and the contents of the residual dichloromethane, cyclohexane, n-heptane and o-xylene in the vinyl sulfate are obtained, wherein the formula (1) is as follows: wi ═ [ (Y-b)/(a × C)Sample (A))]X 100%, where wi is the residual content of dichloromethane, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; y is the chromatographic peak area of residual dichloromethane, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; b is the intercept of working curves of dichloromethane, cyclohexane, n-heptane and o-xylene; a is the slope of a working curve of dichloromethane, cyclohexane, n-heptane and o-xylene; cSample (A)Is the concentration of the vinyl sulfate sample, mg/mL.
Example 1
1. Preparation of sample solution
A0.5 g sample of vinyl sulfate was weighed, and 5mL of a sample solution obtained by dissolving chlorobenzene was added. Each sample batch was prepared in duplicate.
2. Preparation of Standard solutions
Accurately weighing a standard substance 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 the chlorobenzene in a 50mL volumetric flask, fixing the volume, uniformly mixing, respectively and precisely transferring 0.2mL, 0.5mL and 1.0mL of the solution into 3 100mL volumetric flasks, fixing the volume with the chlorobenzene, uniformly mixing to obtain 3 standard solutions, respectively measuring as 1 standard solution, wherein the concentration of the dichloromethane is 0.02mg/mL, the concentration of the cyclohexane is 0.02mg/mL, the concentration of the n-heptane is 0.02mg/mL, and the concentration of the o-xylene is 0.02 mg/mL; the concentration of dichloromethane of the standard solution 2 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 0.05 mg/mL; standard solution 3, the concentration of methylene chloride is 0.10mg/mL, the concentration of cyclohexane is 0.10mg/mL, the concentration of n-heptane is 0.10mg/mL, and the concentration of o-xylene is 0.10 mg/mL.
3. Measurement of
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 determining the contents of dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution by adopting an external standard method for quantitative determination. The gas chromatograms of the specific measurement results are shown in fig. 1 and 2, and it can be seen from fig. 1 and 2 that the separation effect of dichloromethane, 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 corresponding dichloromethane, cyclohexane, n-heptane and o-xylene, draw corresponding standard working curves, and calculate regression equations of the standard working curves of dichloromethane, cyclohexane, n-heptane and o-xylene. And performing 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 curve of the corresponding dichloromethane, cyclohexane, n-heptane and o-xylene, and calculating to obtain the concentrations of the dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution.
Wherein, the detection conditions of the headspace are as follows: the temperature of the head space furnace is 100 ℃; the balance time of the headspace furnace is 30 min. In the gas chromatography-flame ionization detector method, the adopted temperature-raising procedure is as follows: the initial temperature was 50 ℃ for 2min, and the temperature was raised to 240 ℃ at a rate of 10 ℃/min for 5 min.
The detection conditions of the gas chromatography-flame ionization detector method are as follows: the chromatographic column is a DB-624 column (30m × 0.32mm × 1.8 μm, column length × inner diameter × stationary phase membrane thickness), and the packing is chemically bonded 6% cyanopropylbenzene + 94% methylpolysiloxane; the detector is a flame ionization detector (hydrogen flame detector, FID) with a detector temperature of 260 ℃; the temperature of a sample inlet is 250 ℃; the sample injection amount is 1.0 mL; the carrier gas is high-purity helium, and the purity of the carrier gas is more than or equal to 99.999 percent; the flow rate of the carrier gas is 2.0 mL/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 the formula (1), and the contents of the residual dichloromethane, cyclohexane, n-heptane and o-xylene in the vinyl sulfate are obtained, wherein the formula (1) is as follows: wi ═ [ (Y-b)/(a × C)Sample (A))]X 100%, where wi is the residual content of dichloromethane, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; y is the chromatographic peak area of residual dichloromethane, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; b is the intercept of working curves of dichloromethane, cyclohexane, n-heptane and o-xylene; a is the slope of a working curve of dichloromethane, cyclohexane, n-heptane and o-xylene; cSample (A)Is the concentration of the vinyl sulfate sample, mg/mL.
Example 2
The series of standard solutions with different concentrations prepared in step 2 of example 1 were subjected to HS-GC-FID analysis with the chromatographic peak areas of dichloromethane, cyclohexane, n-heptane, and o-xylene as ordinate (Y-axis) and the concentrations of the corresponding dichloromethane, cyclohexane, n-heptane, and o-xylene as abscissa (X-axis) to obtain regression equations and correlation coefficients of dichloromethane, cyclohexane, n-heptane, and o-xylene, as shown in table 1. As can be seen from Table 1, the linear relationship of the standard curves of dichloromethane, cyclohexane, n-heptane and o-xylene is good, and the correlation coefficient r is larger than 0.999. The matrix with the lowest concentration is matched with the standard solution for 10 times of HS-GC-FID parallel detection analysis, the concentration corresponding to 3 times of signal to noise ratio is taken as the detection limit, the detection limit of dichloromethane is 0.03 mu g/mL, the detection limit of cyclohexane is 0.005 mu g/mL, the detection limit of n-heptane is 0.01 mu g/mL, and the detection limit of o-xylene is 0.05 mu g/mL, and the method has higher sensitivity.
TABLE 1
Note: y: peak area; x: concentration of
Example 3
Taking 3 finished vinyl sulfate product samples produced by different manufacturers respectively, wherein the serial numbers are No. 1, No. 2 and No. 3, preparing a sample solution and a standard solution according to the step 1 and the step 2 in the embodiment 1, measuring according to the step 3 in the embodiment 1, and respectively calculating the solvent residue contents of dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution according to the formula (1). Each sample was assayed in 5 replicates and the results calculated are shown in tables 2-5. As can be seen from tables 2-5, this method determines dichloromethane in vinyl sulfate with RSD < 5%; the result of measuring cyclohexane in the vinyl sulfate is RSD less than 6 percent; the result of measuring the n-heptane in the vinyl sulfate is RSD less than 4 percent; the precision of the measuring result is high, and the reproducibility is good.
Table 2 results of accuracy of dichloromethane in sample solutions (n ═ 5)
Table 3 precision results of cyclohexane in sample solutions (n ═ 5) confirmation data
Table 4 results of precision of n-heptane (n-5) in sample solutions confirmed data
Table 5 results of precision of o-xylene in sample solutions (n-5) confirmed data
Example 4
Taking a sample numbered as # 1 in example 3, preparing a sample solution according to step 1 in example 1 and preparing a standard solution according to step 2, wherein the sample is dissolved by the standard solution 2 in step 2 instead of chlorobenzene, and measuring according to step 3 in example 1, calculating the residual content of the solvent in the sample solution by the formula (1). The results were obtained in 5 replicates and the calculated recoveries are shown in Table 6. As can be seen from Table 6, the average recovery rate of the process was 90-110%, and the process accuracy was high.
Table 6 method accuracy test results (n-5) confirmation data
Example 5
The sample No. 1 in example 3 was sampled, the sample solution prepared in step 1 and the standard solution prepared in step 2 in example 1 were used, and the results are shown in Table 7 when the HS-GC-FID was used for detection.
TABLE 7 confirmation data of measurement results of different temperature setting programs
| Temperature program | Set temperature (. degree. C.) | Test time/min | Peak out situation |
| Isothermal procedure | 80℃ | 50 | Long time consumption and poor peak shape of chlorobenzene |
| Isothermal procedure | 120℃ | 30 | Chlorobenzene can not be separated from o-xylene |
| Isothermal procedure | 150℃ | 30 | Dichloromethane and cyclohexane can not be separated |
| Isothermal procedure | 220 |
20 | Dichloromethane and cyclohexane, and n-heptane can not be separated from blank peak of reagent |
| Temperature program | See example 1 | 26 | Effective separation of main peak from all solvents to be tested |
As can be seen from table 7, by integrating the degrees of separation, peak shapes, and test times of the main peak and the relevant solvent to be tested, the main peak and the relevant solvent to be tested can be effectively separated when the temperature raising program with the preferred conditions is adopted in the present invention.
In conclusion, the method for detecting the residual solvent in the vinyl sulfate by the headspace gas chromatography provided by the invention can realize complete separation of the related 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. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A method for detecting residual solvent in vinyl sulfate by headspace gas chromatography comprises the following steps: and adding a vinyl sulfate sample into an organic solvent for dissolving to obtain a sample solution, detecting by adopting a headspace-gas chromatography-flame ionization detector method, and determining the content of residual dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution.
2. The method for detecting the residual solvent in the ethylene sulfate by the headspace gas chromatography as claimed in claim 1, wherein the organic solvent is selected from one of chlorobenzene, toluene, diethyl carbonate and ethyl methyl carbonate.
3. The method for detecting residual solvent in vinyl sulfate by headspace gas chromatography as claimed 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.
4. The method for detecting residual solvent in vinyl sulfate by headspace gas chromatography as claimed in claim 1, wherein the detection is performed by headspace-gas chromatography-flame ionization detector method, comprising the following steps:
1) preparing a standard solution: taking a standard substance of dichloromethane, cyclohexane, n-heptane and o-xylene, adding an organic solvent for dissolving, and then fixing the volume to prepare a standard solution;
2) sample detection: respectively detecting the standard solution and the sample solution by adopting a headspace-gas chromatography-flame ionization detector method, comparing retention time for qualitative determination, and determining the contents of dichloromethane, cyclohexane, n-heptane and o-xylene in the sample solution by adopting an external standard method for quantitative determination.
5. The method for detecting the residual solvent in the vinyl sulfate by headspace gas chromatography as claimed in claim 4, wherein in the step 1), the ratio of the mass of the added dichloromethane, cyclohexane, n-heptane, o-xylene standard substance to the volume of the added 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.
6. The method for detecting the residual solvent in the vinyl sulfate by using the headspace gas chromatography as claimed in claim 4, wherein in the step 1), the concentration of the dichloromethane in the standard solution is 0.02-0.1mg/mL, the concentration of the cyclohexane in the standard solution is 0.02-0.1mg/mL, the concentration of the n-heptane in the standard solution is 0.02-0.1mg/mL, and the concentration of the o-xylene in the standard solution is 0.02-0.1 mg/mL.
7. The method for detecting residual solvent in vinyl sulfate by headspace gas chromatography as claimed in claim 4, wherein in step 2), the detection conditions of the headspace are as follows: the temperature of the head space furnace is 90-110 ℃; the balance time of the top-air furnace is 30-45 min.
8. The method for detecting the residual solvent in the vinyl sulfate according to claim 4, wherein in the step 2), the temperature rising program adopted in the gas chromatography-flame ionization detector method is as follows: the initial temperature is 40-70 deg.C, and is maintained for 1-3min, and the temperature is increased to 240 deg.C at a rate of 5-15 deg.C/min, and is maintained for 5-10 min.
9. The method for detecting residual solvent in vinyl sulfate by headspace gas chromatography as claimed in claim 4, wherein in step 2), the detection conditions of the gas chromatography-flame ionization detector method are as follows: the chromatographic column is a DB-624 column, 20-60m multiplied by 0.18-0.45mm multiplied by 1.0-2.55 mu m, the column length multiplied by the inner diameter multiplied by the thickness of the fixed phase film, and the filler is chemically bonded 6 percent of cyanopropylbenzene and 94 percent of 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 1.0-3.0 mL; the carrier gas is high-purity helium, and the purity of the carrier gas is more than or equal to 99.999 percent; the flow rate of the carrier gas is 1.5-4.0 mL/min; the sample injection mode is split sample injection, and the split ratio is 5-15: 1.
10. The method for detecting the residual solvent in the vinyl sulfate by headspace gas chromatography as claimed in claim 4, wherein in the step 2), the contents of the dichloromethane, the cyclohexane, the n-heptane and the o-xylene in the sample solution are calculated according to the formula (1), so as to obtain the contents of the dichloromethane, the cyclohexane, the n-heptane and the o-xylene remained in the vinyl sulfate, wherein the formula (1) is: wi ═ [ (Y-b)/(a × C)Sample (A))]X 100%, where wi is the residual content of dichloromethane, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; y is the chromatographic peak area of residual dichloromethane, cyclohexane, n-heptane or o-xylene in the vinyl sulfate; b is the intercept of working curves of dichloromethane, cyclohexane, n-heptane and o-xylene; a isThe slope of the working curve of dichloromethane, cyclohexane, n-heptane and o-xylene is shown; cSample (A)Is the concentration of the vinyl sulfate sample, mg/mL.
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