CN114594176B - Method for detecting residual raw materials in aziridine crosslinking agent - Google Patents
Method for detecting residual raw materials in aziridine crosslinking agent Download PDFInfo
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- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002994 raw material Substances 0.000 title claims abstract description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000523 sample Substances 0.000 claims abstract description 54
- 239000012086 standard solution Substances 0.000 claims abstract description 33
- 239000012488 sample solution Substances 0.000 claims abstract description 28
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 239000012490 blank solution Substances 0.000 claims abstract description 19
- 238000002347 injection Methods 0.000 claims abstract description 16
- 239000007924 injection Substances 0.000 claims abstract description 16
- 238000012360 testing method Methods 0.000 claims abstract description 15
- 238000005070 sampling Methods 0.000 claims abstract description 13
- 238000007865 diluting Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000003085 diluting agent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 8
- 238000011067 equilibration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- BEVGWNKCJKXLQC-UHFFFAOYSA-N n-methylmethanamine;hydrate Chemical compound [OH-].C[NH2+]C BEVGWNKCJKXLQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 abstract description 24
- 238000004817 gas chromatography Methods 0.000 abstract description 6
- 239000011550 stock solution Substances 0.000 description 14
- XLJQPXVBQNJNLW-UHFFFAOYSA-N 1-methylaziridine Chemical compound CN1CC1 XLJQPXVBQNJNLW-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002372 labelling Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000036228 toxication Effects 0.000 description 1
Classifications
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- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
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- 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)
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for detecting residual raw materials in an aziridine crosslinking agent, which comprises the following steps: (1) preparing a blank solution: dimethyl sulfoxide is used as a blank solution; (2) preparing a standard solution: dissolving aziridine or methyl aziridine by taking dimethyl sulfoxide as a solvent, and adding a dimethylamine aqueous solution to obtain a standard solution of the aziridine or the methyl aziridine; (3) preparing a sample solution: diluting a cross-linking agent sample to be tested by taking dimethyl sulfoxide as a diluent, and adding a dimethylamine aqueous solution to obtain a sample solution; (4) And (3) respectively testing a blank solution, a standard solution and a sample solution by using a gas chromatograph through headspace sample injection, and calculating the content of aziridine or methyl aziridine in the sample by an external standard one-point method. According to the invention, after the aziridine or methyl aziridine in the sample is derivatized, the content of the aziridine or methyl aziridine is measured by using a headspace sampling gas chromatography, so that the sampling amount can be increased, and the accuracy of a detection result can be improved.
Description
Technical Field
The invention relates to the technical field of organic matter detection, in particular to a method for detecting residual raw materials in an aziridine crosslinking agent.
Background
The aziridine crosslinking agent has good water solubility and oil solubility due to the functional groups and the special molecular structure, and is widely applied to the fields of coating, adhesives, printing ink, imaging, optical fibers, military initiators and the like. The preparation of the aziridine crosslinking agent inevitably uses aziridine or methyl aziridine as a main raw material, and the raw materials have extremely toxic and sensitization due to high volatility, so that the aziridine crosslinking agent is dangerous to the operation and users in the preparation and later use processes, and the detection of the residual aziridine or methyl aziridine raw materials in the product is very important.
Currently, a gas chromatography method is generally adopted in the detection method of aziridine substances, for example, the method disclosed in the Chinese patent literature for directly and accurately detecting the residual amount of aziridine in a light industrial product is disclosed in the publication No. CN104458962B, and the aziridine is firstly dissolved and taken out from the light industrial product by using isooctane, and then detected by using the gas chromatography.
However, because the aziridine crosslinking agent is easy to coagulate in the chromatographic column, when the residual raw materials in the aziridine crosslinking agent are detected by gas chromatography in the prior art, the product is usually diluted in a large amount, and then microscale sample injection is carried out to prevent the crosslinking agent from coagulating in the chromatographic column to damage the chromatographic column. However, the diluted concentration of the product is too low, so that the detection difficulty of the (methyl) aziridine is high, and the hidden danger is buried for the subsequent use of the crosslinking agent.
Disclosure of Invention
The invention provides a method for detecting residual raw materials in an aziridine crosslinking agent, which aims to solve the problems that when the residual raw materials in the aziridine crosslinking agent are detected by using a gas chromatography in the prior art, a large amount of dilution is needed to be carried out on a sample so as to prevent the crosslinking agent from condensing in a chromatographic column, but the concentration of the sample is too low, so that the detection difficulty of aziridine substances is relatively high.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A method for detecting residual raw materials in an aziridine crosslinking agent, comprising the steps of:
(1) Preparing a blank solution: dimethyl sulfoxide is used as a blank solution;
(2) Preparing a standard solution: dissolving aziridine or methyl aziridine by taking dimethyl sulfoxide as a solvent, and adding a dimethylamine aqueous solution to obtain a standard solution of the aziridine or the methyl aziridine;
(3) Preparing a sample solution: diluting a cross-linking agent sample to be tested by taking dimethyl sulfoxide as a diluent, and adding a dimethylamine aqueous solution to obtain a sample solution;
(4) And (3) respectively testing a blank solution, a standard solution and a sample solution by using a gas chromatograph through headspace sample injection, and calculating the content of aziridine or methyl aziridine in the sample by an external standard one-point method.
According to the invention, the residual raw materials in the aziridine crosslinking agent are detected by the gas chromatography of headspace sampling, and compared with a conventional sampling method, the headspace sampling can improve the sampling amount of a sample, and the influence on a detection result after the sample is diluted to a lower concentration is avoided. However, because the aziridine and the methyl aziridine are unstable at high temperature, the detection limit is higher when headspace sampling is directly adopted, and therefore, the (methyl) aziridine is derivatized by adding dimethylamine aqueous solution when preparing standard solution and sample solution. Under the catalysis of water, (methyl) aziridine can react with dimethylamine to generate N, N-dimethyl ethylenediamine, thereby improving the high temperature stability of the (methyl) aziridine and reducing the detection limit. Meanwhile, the invention adopts dimethyl sulfoxide as a solvent to prepare a standard solution and a sample solution, the boiling point of the dimethyl sulfoxide is high, and the separation degree of the detected substances is good; and the dimethyl sulfoxide has good water solubility, and can be mixed with a sample, dimethylamine and aziridine, so that the whole system is uniform, and the accuracy of a detection result is improved.
Therefore, the method provided by the invention is used for detecting the residual (methyl) aziridine in the aziridine crosslinking agent, so that the sample injection amount is increased, the detection sensitivity is improved, and the repeatability is good; the detection limit of the (methyl) aziridine is reduced, the accuracy of the detection result is improved, the response is good, and the danger of the cross-linking agent in the subsequent use process is greatly reduced.
Preferably, the mass concentration of the dimethylamine aqueous solution in the step (2) is 30-40%; the mass ratio of dimethylamine to aziridine or methyl aziridine in the standard solution is 1:0.1-0.2.
Preferably, the standard solution obtained in the step (2) has a concentration of 0.01 to 0.02mg/mL.
Preferably, the standard solution in the step (2) is prepared by the following steps: mixing aziridine or methyl aziridine with dimethylamine water solution, adding dimethyl sulfoxide, ultrasonically oscillating at 25-30 ℃ for 5-10 min, and then fixing the volume by using the dimethyl sulfoxide to obtain the standard solution. The boiling point of the added dimethylamine is lower, and excessive rest dimethylamine can be discharged after ultrasonic oscillation at 25-30 ℃ so as to avoid influencing the detection result.
Preferably, the mass concentration of the dimethylamine aqueous solution in the step (3) is 30-40%; the mass ratio of dimethylamine to the cross-linking agent sample in the sample solution is 1:10-15.
Preferably, the concentration of the sample solution obtained in the step (3) is 5 to 100mg/mL.
Preferably, the preparation method of the sample solution in the step (3) comprises the following steps: and mixing the cross-linking agent sample to be detected with dimethylamine aqueous solution, adding dimethyl sulfoxide, carrying out ultrasonic oscillation at 25-30 ℃ for 5-10 min, and then using the dimethyl sulfoxide to fix the volume to obtain the sample solution.
Preferably, the headspace sampling parameters in step (4) are: sample cell temperature: 100+/-2 ℃; quantitative ring temperature: 110+/-2 ℃; temperature of the transfer tube: 120+/-2 ℃; headspace heating equilibration time: 30+/-5 min; headspace bottle pressurization time: 0.08 to 0.12min; quantitative loop quantitative time: 0.08 to 0.12min; quantitative loop equilibration time: 0.05min; sample introduction time: 0.40 to 0.60min.
Preferably, the parameters of the gas chromatograph in step (4) are: chromatographic column: DB-624, 30 mX0.53 mm X3.0 μm; injector temperature: 250+/-5 ℃; split ratio: 30:1; column flow rate: 0.8-1.2 mL/min; carrier gas: n 2; detector temperature: 260+/-5 ℃; detector conditions: h 2:30mL/min;Air:300mL/min;N2:14 mL/min.
Preferably, the temperature rise degree of the gas chromatograph in the step (4) is: keeping for 2.8-3.2 min at the initial temperature of 50+/-2 ℃; then heating to 80+/-5 ℃ at the speed of 10 ℃/min, and keeping for 0.8-1.2 min; then heating to 120+/-5 ℃ at the speed of 30 ℃/min, and keeping for 4.8-5.2 min.
Therefore, the invention has the following beneficial effects:
(1) By adopting a headspace sampling method, the sampling amount of a sample can be increased, and the influence on a detection result caused by diluting the sample to a lower concentration in the traditional sampling method is avoided;
(2) The (methyl) aziridine is derivatized by adding dimethylamine aqueous solution when preparing standard solution and sample solution, so that the high-temperature stability of the (methyl) aziridine is improved, and the detection limit is reduced.
Drawings
FIG. 1 is a chromatogram of a blank solution of example 1 of the present invention.
FIG. 2 is a chromatogram of 6 standard solutions for evaluation of system suitability in example 1 of the present invention.
FIG. 3 is a chromatogram of 6 injections in the limit of amount test of example 1 of the present invention.
FIG. 4 is a chromatogram of each concentration of standard solution in a linear assay of example 1 of the present invention.
Fig. 5 is a linear fit plot in a linear test of example 1 of the present invention.
FIG. 6 is a chromatogram of each of the labeled concentration samples in the accuracy test of example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and detailed description.
General examples:
A method for detecting residual raw materials in an aziridine crosslinking agent, comprising the steps of:
(1) Preparing a blank solution: dimethyl sulfoxide is used as a blank solution;
(2) Preparing a standard solution: mixing aziridine or methyl aziridine with 30-40% dimethylamine water solution in the weight ratio of 1 to 0.1-0.2; adding dimethyl sulfoxide, carrying out ultrasonic oscillation at 25-30 ℃ for 5-10 min, and then fixing the volume by using the dimethyl sulfoxide to obtain an aziridine or methyl aziridine standard solution with the concentration of 0.01-0.02 mg/mL;
(3) Preparing a sample solution: mixing a cross-linking agent sample to be detected with 30-40% dimethylamine water solution, wherein the mass ratio of dimethylamine to the cross-linking agent sample is 1:10-15; adding dimethyl sulfoxide, carrying out ultrasonic oscillation at 25-30 ℃ for 5-10 min, and then fixing the volume by using the dimethyl sulfoxide to obtain a sample solution with the concentration of 5-100 mg/mL;
(4) Respectively testing a blank solution, a standard solution and a sample solution by using a gas chromatograph through headspace sample injection, and calculating the content of aziridine or methyl aziridine in the sample by an external standard one-point method;
Wherein, headspace sampling parameters are: sample cell temperature: 100+/-2 ℃; quantitative ring temperature: 110+/-2 ℃; temperature of the transfer tube: 120+/-2 ℃; headspace heating equilibration time: 30+/-5 min; headspace bottle pressurization time: 0.08 to 0.12min; quantitative loop quantitative time: 0.08 to 0.12min; quantitative loop equilibration time: 0.05min; sample introduction time: 0.40 to 0.60min;
The parameters of the gas chromatograph are: chromatographic column: DB-624, 30 mX0.53 mm X3.0 μm; injector temperature: 250+/-5 ℃; split ratio: 30:1; column flow rate: 0.8-1.2 mL/min; carrier gas: n 2; detector temperature: 260+/-5 ℃; detector conditions: h 2:30mL/min;Air:300mL/min;N2:14 mL/min; the temperature rise degree is as follows: keeping for 2.8-3.2 min at the initial temperature of 50+/-2 ℃; then heating to 80+/-5 ℃ at the speed of 10 ℃/min, and keeping for 0.8-1.2 min; then heating to 120+/-5 ℃ at the speed of 30 ℃/min, and keeping for 4.8-5.2 min.
Example 1:
A method for detecting residual raw materials in an aziridine crosslinking agent, comprising the steps of:
(1) Preparing a blank solution: dimethyl sulfoxide is used as a blank solution;
(2) Preparing a standard solution: taking 100mg of aziridine, placing the aziridine into a 100mL volumetric flask, adding 1g of dimethylamine aqueous solution with the mass concentration of 40%, adding 10mL of dimethyl sulfoxide, carrying out ultrasonic oscillation at 25 ℃ for 5min, and then using the dimethyl sulfoxide to fix the volume to a scale; weighing 10mL of the prepared solution, adding the solution into a 100mL volumetric flask, and fixing the volume to a scale by using dimethyl sulfoxide to obtain a standard stock solution of aziridine with the concentration of 0.1 mg/mL; measuring 10mL of standard stock solution, adding the stock solution into a 100mL volumetric flask, and fixing the volume to a scale by using dimethyl sulfoxide to obtain an aziridine standard solution with the concentration of 0.01 mg/mL;
(3) Preparing a sample solution: taking 500mg of a cross-linking agent sample to be detected, putting the cross-linking agent sample into a 100mL volumetric flask, adding 1g of a dimethylamine aqueous solution with the mass concentration of 40%, adding 10mL of dimethyl sulfoxide, carrying out ultrasonic oscillation at 25 ℃ for 10min, and then using the dimethyl sulfoxide to fix the volume to obtain a sample solution with the concentration of 5 mg/mL;
(4) And (3) respectively testing a blank solution, a standard solution and a sample solution by using a gas chromatograph through headspace sample injection, and calculating the content of aziridine in the sample by using an external standard one-point method.
The headspace sampler is set as follows:
The settings of the gas chromatograph were as follows:
1. The system applicability evaluation method comprises the following steps: taking 10mL of each of the blank solution and 6 parts of standard solution, respectively adding the blank solution and the 6 parts of standard solution into a 20mL headspace bottle, and carrying out sample injection detection. The evaluation results are shown in FIGS. 1 to 2 and Table 1.
Table 1: and evaluating the system applicability.
As can be seen from fig. 1, there is no interference around the target peak position of the blank solution; as can be seen from FIG. 2 and Table1, the relative standard deviation RSD% of the aziridine peak area in the chromatograms obtained 6 times from the standard solution is less than or equal to 15.0%, and the method in the invention meets the system applicability requirement.
2. Quantitative limit test
And (3) diluting the standard stock solution of the aziridine obtained in the step (2) into different concentrations for sample injection detection, and comparing signals measured by the samples with noise signals to obtain the concentration of 1 mug/mL with a signal-to-noise ratio of about 10:1.
Accurately measuring 1mL of standard stock solution, putting the standard stock solution into a 100mL volumetric flask, and fixing the volume to a scale by using dimethyl sulfoxide; precisely measuring 10mL of solution, placing the solution in a 20mL headspace bottle, carrying out sample injection detection, and continuously carrying out sample injection for 6 times; the detection results are shown in fig. 3 and table 2.
Table 2: and quantifying the limit test results.
As can be seen from FIG. 3 and Table 2, the peak area RSD% value of the sample was not more than 25% at a concentration of 1.012. Mu.g/mL for 6 continuous injections, satisfying the requirements, indicating that the quantitative limit of the method in the present invention was 1. Mu.g/mL.
3. Linearity test
Measuring 3mL, 5mL, 7.5mL, 10mL, 12.5mL and 15mL of the standard stock solution of the aziridine obtained in the step (2), respectively placing the stock solutions in a 100mL volumetric flask, and fixing the volume to the scale by using dimethyl sulfoxide, wherein the solution is prepared as follows:
10mL of each solution obtained above was measured and added to a 20mL headspace bottle, and sample injection detection was performed, and the results are shown in FIGS. 4 to 5 and Table 3.
Table 3: and (5) linearly testing the result.
As can be seen from FIGS. 4 to 5 and Table 3, the method of the present invention satisfies the linearity requirement in the linear concentration range of 30 to 150% with a correlation coefficient of 0.99 or more.
4. Accuracy test
Performing a labeling recovery test on the sample solution obtained in the step (3), and evaluating the accuracy of the method through the labeling recovery rate; the preparation method of the standard adding solution with each concentration comprises the following steps:
Blank: taking 500mg of a cross-linking agent sample to be detected, putting the cross-linking agent sample into a 100mL volumetric flask, adding 1g of a 40% dimethylamine aqueous solution by mass concentration, adding 10mL dimethyl sulfoxide, carrying out ultrasonic vibration at 25 ℃ for 10min, and then using the dimethyl sulfoxide to fix the volume to obtain a blank sample solution.
50% Of the labeling solution: taking 500mg of a cross-linking agent sample to be detected, putting the cross-linking agent sample into a 100mL volumetric flask, adding 1g of a 40% dimethylamine aqueous solution by mass concentration, adding 10mL of dimethyl sulfoxide, carrying out ultrasonic vibration at 25 ℃ for 10min, adding 5mL of the standard stock solution obtained in the step (2), and fixing the volume to a scale by using the dimethyl sulfoxide.
100% Of the labeling solution: taking 500mg of a cross-linking agent sample to be detected, putting the cross-linking agent sample into a 100mL volumetric flask, adding 1g of a 40% dimethylamine aqueous solution by mass concentration, adding 10mL of dimethyl sulfoxide, carrying out ultrasonic vibration at 25 ℃ for 10min, adding 10mL of the standard stock solution obtained in the step (2), and fixing the volume to a scale by using the dimethyl sulfoxide.
150% Of addition standard solution: taking 500mg of a cross-linking agent sample to be detected, putting the cross-linking agent sample into a 100mL volumetric flask, adding 1g of a 40% dimethylamine aqueous solution by mass concentration, adding 10mL of dimethyl sulfoxide, carrying out ultrasonic vibration at 25 ℃ for 10min, adding 15mL of the standard stock solution obtained in the step (2), and fixing the volume to a scale by using the dimethyl sulfoxide.
10ML of the above solution was placed in a 20mL headspace bottle, and sample was introduced for detection, and the results are shown in FIG. 6 and Table 4.
Table 4: and (5) testing a result of accuracy.
As can be seen from fig. 6 and table4, the method of the present invention has good accuracy.
Comparative example 1:
in the case of preparing the standard solution and the sample solution in comparative example 1, the dimethylamine aqueous solution was not added, and the other components were the same as in example 1.
The limit of quantification in comparative example 1 was tested by:
Preparing standard stock solution: taking 100mg of aziridine, placing the aziridine into a volumetric flask of 100mL, and fixing the volume to the scale by using dimethyl sulfoxide; weighing 10mL of the prepared solution, adding the solution into a 100mL volumetric flask, and fixing the volume to a scale by using dimethyl sulfoxide to obtain a standard stock solution of aziridine with the concentration of 0.1 mg/mL;
1. Mu.g/ml of an aziridine solution was prepared: 1mL of standard stock solution is accurately measured, placed into a 100mL volumetric flask, and the volume is fixed to the scale by dimethyl sulfoxide to obtain an aziridine solution with the concentration of 1 mug/mL. And precisely measuring 10mL of aziridine solution, placing the aziridine solution in a 20mL headspace bottle, carrying out sample injection detection, and continuously carrying out sample injection for 6 times.
The peak areas obtained by 6 times of detection are as follows: 170-191, which is much smaller than the average 408.67 in example 1. Therefore, the signal to noise ratio in comparative example 1 is less than 10, the relative sensitivity is poor, and the quantitative limit requirement cannot be met.
Claims (10)
1. The method for detecting the residual raw materials in the aziridine crosslinking agent is characterized by comprising the following steps of:
(1) Preparing a blank solution: dimethyl sulfoxide is used as a blank solution;
(2) Preparing a standard solution: dissolving aziridine or methyl aziridine by taking dimethyl sulfoxide as a solvent, and adding a dimethylamine aqueous solution to obtain a standard solution of the aziridine or the methyl aziridine; the mass ratio of dimethylamine to aziridine or methyl aziridine in the standard solution is 1:0.25;
(3) Preparing a sample solution: diluting a cross-linking agent sample to be tested by taking dimethyl sulfoxide as a diluent, and adding a dimethylamine aqueous solution to obtain a sample solution; the mass ratio of dimethylamine to the cross-linking agent sample in the sample solution is 1:1.25;
(4) And (3) respectively testing a blank solution, a standard solution and a sample solution by using a gas chromatograph through headspace sample injection, and calculating the content of aziridine or methyl aziridine in the sample by an external standard one-point method.
2. The method for detecting residual raw materials in an aziridine crosslinking agent according to claim 1, wherein the mass concentration of the dimethylamine aqueous solution in the step (2) is 30-40%.
3. The method for detecting residual raw materials in an aziridine crosslinking agent according to claim 1, wherein the standard solution concentration obtained in the step (2) is 0.01-0.02 mg/mL.
4. A method for detecting residual raw materials in an aziridine-based crosslinking agent according to claim 1,2 or 3, wherein the standard solution preparation method in step (2) is as follows: mixing aziridine or methyl aziridine with dimethylamine water solution, adding dimethyl sulfoxide, carrying out ultrasonic oscillation at 25-30 ℃ for 5-10 min, and then fixing the volume by using the dimethyl sulfoxide to obtain the standard solution.
5. The method for detecting residual raw materials in an aziridine crosslinking agent according to claim 1, wherein the mass concentration of the dimethylamine aqueous solution in the step (3) is 30-40%.
6. The method for detecting residual raw materials in an aziridine crosslinking agent according to claim 1, wherein the concentration of the sample solution obtained in the step (3) is 5-100 mg/mL.
7. The method for detecting residual raw materials in an aziridine crosslinking agent according to claim 1, 5 or 6, wherein the preparation method of the sample solution in the step (3) is as follows: and mixing a cross-linking agent sample to be detected with a dimethylamine aqueous solution, adding dimethyl sulfoxide, carrying out ultrasonic oscillation at 25-30 ℃ for 5-10 min, and then using the dimethyl sulfoxide to fix the volume to obtain the sample solution.
8. The method for detecting residual raw materials in an aziridine crosslinking agent according to claim 1, wherein the headspace sampling parameters in step (4) are as follows: sample cell temperature: 100+/-2 ℃; quantitative ring temperature: 110+/-2 ℃; temperature of the transfer tube: 120+/-2 ℃; headspace heating equilibration time: 30+/-5 min; headspace bottle pressurization time: 0.08-0.12 min; quantitative loop quantitative time: 0.08-0.12 min; quantitative loop equilibration time: 0.05min; sample introduction time: 0.40 to 0.60min.
9. The method for detecting residual raw materials in an aziridine-based crosslinking agent according to claim 1, wherein the parameters of the gas chromatograph in step (4) are: chromatographic column: DB-624, 30m x 0.53mm x 3.0 [ mu ] m; injector temperature: 250+/-5 ℃; split ratio: 30:1; column flow rate: 0.8-1.2 mL/min; carrier gas: n 2; detector temperature: 260+/-5 ℃; detector conditions: h 2: 30mL/min; Air: 300mL/min; N2:14 mL/min.
10. The method for detecting residual raw materials in an aziridine-based crosslinking agent according to claim 1 or 9, wherein the temperature rise degree of the gas chromatograph in the step (4) is: keeping for 2.8-3.2 min at an initial temperature of 50+/-2 ℃; then heating to 80+/-5 ℃ at the speed of 10 ℃/min, and keeping for 0.8-1.2 min; and then heating to 120+/-5 ℃ at the speed of 30 ℃/min, and keeping for 4.8-5.2 min.
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