CN114216977B - Gas chromatography-mass spectrometry (GC-MS) determination method and application thereof - Google Patents
Gas chromatography-mass spectrometry (GC-MS) determination method and application thereof Download PDFInfo
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 28
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims abstract description 91
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000000605 extraction Methods 0.000 claims abstract description 46
- 238000001514 detection method Methods 0.000 claims abstract description 34
- 239000003973 paint Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000002137 ultrasound extraction Methods 0.000 claims description 29
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 238000004817 gas chromatography Methods 0.000 claims description 12
- 239000012159 carrier gas Substances 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 4
- 238000004949 mass spectrometry Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 32
- 239000000126 substance Substances 0.000 abstract description 13
- 230000004044 response Effects 0.000 abstract description 7
- 238000002372 labelling Methods 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- -1 tetraethylene glycol dimethyl ether tri-hydrate Chemical compound 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000011835 investigation Methods 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000012224 working solution Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000002740 effect on eyes Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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Abstract
The invention discloses a gas chromatography-mass spectrometry determination method of tetraethylene glycol dimethyl ether and application thereof, belonging to the technical field of chemical detection, and the gas chromatography-mass spectrometry determination method of the tetraethylene glycol dimethyl ether provided by the invention comprises the following steps: extracting a sample to be detected in acetonitrile, filtering, and carrying out gas chromatography-mass spectrometry combined detection on the obtained filtrate; the technical scheme of the invention adopts a pretreatment mode of acetonitrile extraction, so that the extraction recovery rate can reach more than 95 percent; the technical scheme provided by the invention can obtain symmetrical tetraethylene glycol dimethyl ether chromatographic peaks with no interference and high response value within 7.8min, so that the detection time is obviously shortened, and the detection efficiency is improved; meanwhile, the determination method provided by the technical scheme of the invention has the advantages of low detection limit, good precision and high sample labeling recovery rate, and can be directly applied to the detection of the tetraethylene glycol dimethyl ether in the water-based paint.
Description
Technical Field
The invention belongs to the technical field of chemical detection, and particularly relates to a gas chromatography-mass spectrometry determination method of tetraethylene glycol dimethyl ether and application thereof.
Background
Tetraethylene glycol dimethyl ether (TETRAETHYLENE GLYCOL DIMETHYL ETHER), also known as methyl-tetraethylene glycol-methyl, tetraethylene glycol dimethyl ether tri-hydrate, tetraethylene glycol dimethyl ether tetra-hydrate, bis [2- (2-methoxyethoxy) ethyl ] ether and the like, has a structure shown in a formula I, a molecular formula of C 10H22O5, and CAS number of 143-24-8, is an aprotic solvent, and is commonly used as a solvent for paint binder production, a coagulant in a paint formula, an emulsifier in ink, an HFC/CFC lubricant in an automobile air conditioner compressor and the like.
Although the tetraethylene glycol dimethyl ether has the advantages of good performance, economy, wide adaptability and the like, researches prove that the tetraethylene glycol dimethyl ether has strong stimulation effect on eyes and certain reproduction toxicity; the european union chemical registration, assessment, authorization and restriction regulations ((EC No 1907/2006, abbreviated REACH) list of highly interesting Substances (SVHC) that when the substance mass fraction in the SVHC candidate list is more than 0.1% and the substance enters the european union more than 1 ton/year/company each year, the manufacturer or importer of the substance must notify the european union chemical administration, it is necessary to establish a suitable method to determine the content of the substance in the product, according to the regulation of REACH clause 7.2; however, the detection of the residues of tetraethylene glycol dimethyl ether in the product is rarely reported at present; wherein in the prior art, (1) Zhaofu, lv Meng, GC-MS method is used for simultaneously measuring benzene series, glycol ether and ester compounds thereof in the water-based paint; (2) Du Weifeng, li Xiuying, et al, gas chromatography-mass spectrometry for simultaneous detection of 5 glycol ethers and esters thereof in cosmetics; (3) Zhou Yuyan, cheng Yuxiao, et al, gas chromatography-mass spectrometry (GC-MS) simultaneously measure five glycol ethers and ester compounds thereof in water-based paint, and gas chromatography-mass spectrometry (GC-MS) is performed on analogues, but firstly, the content of glycol ethers and ether esters thereof in non-water-based paint or cosmetics and the like is studied in the prior art, the content of tetraethyleneglycol dimethyl ether in water-based paint is not directly studied, and secondly, most of the prior art adopts methanol as a solvent, direct constant volume extraction is performed, and the analysis time by a GC-MS or GC-FID instrument is long, so that the research efficiency is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a rapid and accurate gas chromatography-mass spectrometry determination method for tetraethylene glycol dimethyl ether and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a gas chromatography-mass spectrometry method for tetraethylene glycol dimethyl ether comprises the following steps:
(1) Extracting a sample to be detected in acetonitrile, and filtering to obtain filtrate;
(2) Carrying out gas chromatography-mass spectrometry detection on the filtrate obtained in the step (1);
Wherein, the measurement conditions of the gas chromatography-mass spectrometry are as follows:
Gas chromatography: chromatographic column: agilent DB-WAX; sample inlet temperature: 280 ℃; carrier gas: helium with purity of 99.999% and flow rate of 3mL/min; sample injection mode: not split; chromatographic column flow rate: 1.0-1.5mL/min; heating program: the initial temperature is 60 ℃, kept for 1-2min, and is raised to 230 ℃ at a speed of 15-20 ℃/min and kept for 2min; sample injection amount: 1 μl;
mass spectrometry: ionization mode: EI; ion source temperature: 230 ℃; four-stage bar temperature: 150 ℃, scanning range m/z:10-200 parts; SIM ion m/z: 58. 59, 103.
According to the gas chromatography-mass spectrometry combined detection method provided by the technical scheme of the invention, the pretreatment method of acetonitrile extraction is adopted, so that the extraction recovery rate can reach more than 95%, meanwhile, the analysis time can be obviously shortened to 12 minutes by adopting the gas chromatography-mass spectrometry combined detection provided by the invention, the detection efficiency is improved, and the peak type is symmetrical and smooth, has no interference and has a high response value.
As a preferred embodiment of the gas chromatography-mass spectrometry method, the sample to be measured is an aqueous paint.
As a preferred embodiment of the gas chromatography-mass spectrometry method, the volume ratio of the mass of the sample to be measured to acetonitrile is 2.5g: (8-12) mL.
As a preferred embodiment of the gas chromatography-mass spectrometry method, the volume ratio of the mass of the sample to be measured to acetonitrile is 2.5g:10mL.
When the sample to be measured is water paint and the mass ratio of the water paint to the acetonitrile is in the range, the water paint has good solubility and high extraction recovery rate which can reach more than 95 percent under the acetonitrile extraction condition.
As a preferred embodiment of the gas chromatography-mass spectrometry method of the present invention, the extraction is ultrasonic extraction.
As a preferred implementation mode of the gas chromatography-mass spectrometry method, the temperature of ultrasonic extraction is 40-60 ℃, the times of ultrasonic extraction are 1-2 times, and the time of single ultrasonic extraction is 10-90min.
As a preferred implementation mode of the gas chromatography-mass spectrometry method, the temperature of ultrasonic extraction is 60 ℃, the times of ultrasonic extraction are 2 times, and the time of single ultrasonic extraction is 10min.
In the ultrasonic extraction temperature, the extraction recovery rate of the corresponding tetraethylene glycol dimethyl ether is more than 90 percent, and when the temperature is 60 ℃, the extraction recovery rate can reach 96 percent; when the extraction time is 10 to 90 minutes, the recovery rate of ultrasonic extraction is 90% or more, and therefore, the extraction time is preferably 10 minutes in view of time cost.
As a preferred embodiment of the method for determining the gas chromatography-mass spectrometry, the filtration is performed by a filter membrane, and the pore size of the filter membrane is 0.45 μm.
As a preferred embodiment of the method for determining gas chromatography according to the present invention, the gas chromatography conditions are as follows: chromatographic column: 30m 0.25mm,0.25 μm Agilent DB-WAX; chromatographic column flow rate: 1.0mL/min; heating program: the initial temperature was 60℃for 1min, and was raised to 230℃at a rate of 20℃per min and maintained for 2min.
When the preferable chromatographic column flow and the temperature rise program are the parameters, the response value and the symmetry of the peak can be further improved, the peak time can be advanced, the detection time can be shortened, and the detection efficiency can be improved.
In addition, the invention also provides application of the gas chromatography-mass spectrometry detection method in detecting the content of tetraethylene glycol dimethyl ether in the water-based paint.
Compared with the prior art, the invention has the beneficial effects that:
First: according to the gas chromatography-mass spectrometry method for tetraethyl glycol dimethyl ether provided by the technical scheme of the invention, the pretreatment mode of ultrasonic extraction of acetonitrile at 60 ℃ is adopted, so that the extraction recovery rate can reach more than 95%;
Second,: under the chromatographic conditions and the mass spectrum conditions provided by the technical scheme of the invention, the symmetrical chromatographic separation peak of the tetraethylene glycol dimethyl ether can be obtained within 7.8min, the total analysis time is within 12min, the detection time is obviously shortened, the detection efficiency is improved, and the obtained peak is symmetrical and smooth, has no interference and has high response value under the detection conditions;
Third,: the determination method provided by the technical scheme of the invention has the advantages of low detection limit, good precision and high sample labeling recovery rate; the correlation coefficient reaches 0.9989 in the concentration range of 0.5mg/L to 100 mg/L; the detection limit and the quantitative limit are lower and are respectively only 0.016mg/L and 0.055mg/L; RSD% < 1.8%; the average sample labeling recovery rate is 97.1-101.2%, and the method can be directly applied to detection of tetraethylene glycol dimethyl ether in water paint.
Drawings
Fig. 1: a chromatogram of tetraethylene glycol dimethyl ether using an agilent DB-WAX (30 m 0.25mm 0.25 μm) column in example 1;
Fig. 2: a chromatogram of tetraethylene glycol dimethyl ether using an agilent DB-624 (30 m x 0.25mm x 1.4 μm) column in example 1;
fig. 3: a chromatogram of tetraethylene glycol dimethyl ether using an agilent DB-624 (60 m x 0.25mm x 1.4 μm) column in example 1;
fig. 4: a chromatogram of tetraethylene glycol dimethyl ether at the second temperature increase program was used in example 1;
Fig. 5: in example 1, a chromatogram of tetraethylene glycol dimethyl ether was used at a column flow rate of 1.5 mL/min;
Fig. 6: the extraction recovery rate results of different solvents for tetraethylene glycol dimethyl ether in example 2 are shown in the graph;
Fig. 7: the results of the extraction recovery of tetraglyme from the various extraction times in example 2 are plotted.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples; for process parameters not specifically noted, reference may be made to conventional techniques.
The main instruments and reagents used in the examples include:
gas chromatography-mass spectrometry: agilent 7890B-5977A, agilent corporation, USA;
Precision electronic analytical balance: PRACTUM224-1CN, a sensory quantity of 0.1mg, sidoris, germany;
ultrasonic cleaner: KQ-300DE, jiang Dong precision instruments Inc., suzhou;
Standard substance: tetraethylene glycol dimethyl ether, purity 99%, shanghai Ala Biochemical technology Co., ltd;
other reagents: methanol, acetonitrile, toluene, n-hexane and ethyl acetate, all HPLC grade, shanghai's national institute of Electrical and electronics Engineers (CNW).
Example 1
The influence of the change of the gas chromatography condition on the determination of the tetraethylene glycol dimethyl ether is explored in the embodiment, and the method specifically comprises the following three aspects:
1. Chromatographic column exploration
The remaining gas chromatography conditions in this section were: sample inlet temperature: 280 ℃; carrier gas: helium with purity of 99.999% and flow rate of 3mL/min; sample injection mode: not split; chromatographic column flow rate: 1.0mL/min; heating program: the initial temperature is 60 ℃, kept for 1min, and is raised to 230 ℃ at a rate of 20 ℃/min and kept for 2min; sample injection amount: 1. Mu.L, the effect of the change in the column on the analysis results was investigated;
In the experiment, three kinds of chromatographic columns of Agilent DB-WAX (30 m 0.25mm 0.25 μm), agilent DB-624 (30 m 0.25mm 1.4 μm) and Agilent DB-624 (60 m 0.25mm 1.4 μm) are respectively used for analyzing the tetraethylene glycol dimethyl ether, and the obtained chromatograms are shown in fig. 1-3, and as can be seen from fig. 1-3, the peak type of the chromatograms obtained by adopting the analysis of the chromatographic columns of Agilent DB-WAX (30 m 0.25mm 0.25 μm) is smoother and has no interference, so that the chromatographic column of Agilent DB-WAX (30 m 0.25mm 0.25 μm) is preferred as a gas chromatographic analysis column.
2. Temperature program investigation
The remaining gas chromatography conditions in this section were: chromatographic column: agilent DB-WAX (30 m 0.25mm 0.25 μm); sample inlet temperature: 280 ℃; carrier gas: helium with purity of 99.999% and flow rate of 3mL/min; sample injection mode: not split; chromatographic column flow rate: 1.0mL/min; sample injection amount: on the basis of 1 mu L, the influence of the change of a temperature rise program on an analysis result is explored;
In the experiment, two heating programs are respectively used, wherein the initial temperature is 60 ℃, the temperature is kept for 2min, then the temperature is raised to 230 ℃ at the speed of 15 ℃/min and kept for 2min, the initial temperature is kept for 1min, then the temperature is raised to 230 ℃ at the speed of 20 ℃/min and kept for 2min, the chromatogram obtained by the first heating program is shown in figure 1, and the chromatogram obtained by the second heating program is shown in figure 4; as can be seen from fig. 1 and fig. 4, on the basis that other parameters remain unchanged and only the temperature rising program is changed, the peak symmetry of the second temperature rising program is better, the retention time accessory of the second temperature rising program has no impurity peak interference, and meanwhile, the peak time of tetraethylene glycol dimethyl ether in the second temperature rising program is 7.8min earlier, which is 2.7min earlier than the peak time of the first temperature rising program which is 10.5 min; therefore, the second temperature increase program, i.e., the initial temperature of 60℃for 1min, followed by a temperature increase to 230℃for 2min at a rate of 20℃per min, is preferred.
3. Chromatographic column flow exploration
The remaining gas chromatography conditions in this section were: chromatographic column: agilent DB-WAX (30 m 0.25mm 0.25 μm); sample inlet temperature: 280 ℃; carrier gas: helium with purity of 99.999% and flow rate of 3mL/min; sample injection mode: not split; heating program: the initial temperature is 60 ℃, kept for 1min, and is raised to 230 ℃ at a rate of 20 ℃/min and kept for 2min; sample injection amount: on the basis of 1 mul, the influence of the change of the chromatographic column flow on the analysis result is explored;
In the experiment, two chromatographic column flows of 1.0mL/min and 1.5mL/min are respectively adopted, wherein a chromatogram obtained by adopting the chromatographic column flow of 1.0mL/min is shown in a graph in FIG. 4, and a chromatogram obtained by adopting the chromatographic column flow of 1.5mL/min is shown in a graph in FIG. 5; as can be seen from fig. 4 and 5, when the flow rate of the chromatographic column is increased to 1.5mL/min, the peak symmetry of the obtained tetraethyleneglycol dimethyl ether is poor, and the response value is also reduced; therefore, the column flow rate is preferably 1.0mL/min.
Thus, the final preferred conditions for gas chromatography are: chromatographic column: agilent DB-WAX; sample inlet temperature: 280 ℃; carrier gas: helium with purity of 99.999% and flow rate of 3mL/min; sample injection mode: not split; chromatographic column flow rate: 1.0mL/min; heating program: the initial temperature is 60 ℃, kept for 1min, and is raised to 230 ℃ at a rate of 20 ℃/min and kept for 2min; sample injection amount: 1 mul.
Example 2
The embodiment explores the influence of pretreatment conditions of a sample to be detected on the extraction recovery rate of tetraethylene glycol dimethyl ether, and specifically comprises the following aspects:
1. Investigation of extraction solvent
In the part, under the conditions of adopting ultrasonic extraction, the ultrasonic frequency is 2 times, the single ultrasonic time is 10min, and the ultrasonic treatment temperature is 60 ℃, the organic solvent of ultrasonic extraction is changed, and the influence of the organic solvent on the extraction recovery rate is explored;
2.5g of the water-based paint to be measured is respectively weighed and added into 6 organic solvents of 10mL, wherein the 6 organic solvents are acetonitrile, methanol, ethyl acetate, normal hexane, toluene and dichloromethane respectively, then 6 samples are extracted, the extraction efficiency of the 6 organic solvents on the tetraethylene glycol dimethyl ether in the water-based paint is compared, the test result is shown in figure 6, and as can be seen from figure 6, the average extraction efficiency of the acetonitrile on the tetraethylene glycol dimethyl ether in the 6 organic solvents is obviously higher than that of the ethyl acetate, normal hexane and toluene, and is slightly higher than that of the methanol and dichloromethane, and the extraction efficiency is more than 95%; thus, acetonitrile is preferred as the extraction solvent.
2. Investigation of extraction modes
2.5G of water-based paint to be measured is respectively weighed, wherein one part is directly added with acetonitrile and the volume is fixed to 10mL, the other part is added with 10mL of acetonitrile and is subjected to ultrasonic treatment for 10min, and then the recovery rate is detected, wherein the recovery rate of the direct volume fixing treatment is 85%, and the recovery rate of the ultrasonic treatment is 89%; therefore, sonication during extraction is preferred.
3. Investigation of the number of extractions
2.5G of water-based paint to be measured is respectively weighed 2 parts, wherein 10mL of acetonitrile is added into one part, and the mixture is filtered after ultrasonic treatment for 10 min; adding 10mL of acetonitrile into the other part, performing ultrasonic treatment for 10min, taking out the supernatant, adding 10mL of acetonitrile into the residual residue, performing ultrasonic treatment for 10min, filtering, and combining the two filtrates; then, carrying out recovery rate detection on the two obtained filtrate, wherein the recovery rate of the primary ultrasonic treatment is 89%, and the recovery rate of the secondary ultrasonic treatment is 96%; therefore, it is preferable to sonicate twice during extraction.
4. Investigation of extraction temperature
The part researches the influence on the extraction recovery rate of the tetraglyme under different extraction temperatures after the preferential extraction solvent is acetonitrile, the extraction mode is ultrasonic extraction and the times of ultrasonic extraction are 2 times; three temperature gradients were set at 40℃and 50℃and 60℃respectively, and then the extraction recovery was measured, wherein the extraction recovery at 40℃was 90%, the extraction recovery at 50℃was 91% and the extraction recovery at 60℃was 96%, and therefore, the extraction temperature was 60℃was preferred.
5. Investigation of extraction time
In the part, after acetonitrile is preferred as an extraction solvent, ultrasonic extraction is adopted as an extraction mode, the times of ultrasonic extraction are 2 times, the temperature of ultrasonic extraction is 60 ℃, the influence of the time of single extraction on the extraction recovery rate is explored, the extraction time is set to be 10-90min, one gradient is set every 10min, the test result is shown as a graph in fig. 7, the extraction recovery rate is over 90% in the range of 10-90min, and the maximum extraction efficiency can be basically achieved after the ultrasonic time reaches 10min, so that the time of single ultrasonic extraction is preferably 10min.
Thus, the final preferred pretreatment conditions are: acetonitrile is used as a solvent, and the ultrasonic extraction is carried out, wherein the ultrasonic extraction temperature is 60 ℃, the ultrasonic extraction times are 2 times, and the ultrasonic time of single ultrasonic extraction is 10min.
Example 3
In the embodiment, the mass spectrum condition is determined through full scanning; performing full scanning on the prepared tetraethylene glycol dimethyl ether standard working solution with the mass concentration of 10.0mg/L within the range of 10-500 m/z to obtain a total ion flow diagram, and selecting characteristic fragment ions of a substance to be detected as qualitative and quantitative target monitoring ions; thus, the fragment ions m/z 58, 59, 103 of tetraethylene glycol dimethyl ether were finally selected as qualitative ions by scanning in the range of 10-200 m/z, with fragment ion m/z 59 as quantitative ion.
Example 4
1. This example performs the gas chromatography-mass spectrometry determination of tetraethylene glycol dimethyl ether under the most preferred conditions provided in examples 1-4, comprising the steps of:
(1) Preparation of standard solution
I. Standard stock solution: 10mg of tetraethylene glycol dimethyl ether (accurate to 0.1 mg) is accurately weighed by a precision electronic analytical balance, dissolved by acetonitrile and fixed to 10mL to obtain 1000mg/L stock solution, and the stock solution is stored in a refrigerator at 4 ℃.
Ii. Standard working solution: the standard stock solution was diluted stepwise with acetonitrile to obtain 1mg/L, 5mg/L, 10mg/L, 50mg/L, 100mg/L series of standard working solutions.
(2) Pretreatment of a sample to be tested
Weighing 2.5g of water-based paint, placing into a sample bottle, adding 10mL of acetonitrile into the sample bottle, screwing a bottle cap, placing the sample bottle into an ultrasonic cleaner, carrying out ultrasonic treatment at 60 ℃ for 10min, transferring the upper liquid into a 25mL volumetric flask, adding 10mL of acetonitrile into the residual residue, repeating ultrasonic treatment for 10min, combining the filtrates, fixing the volume to a scale with acetonitrile, filtering the extract cooled to room temperature with a filter membrane of 0.45 mu m, filling into a sample injection vial, and carrying out analysis and detection.
(3) Gas chromatography-mass spectrometry test conditions
Gas chromatography: chromatographic column: 30m 0.25mm,0.25 μm Agilent DB-WAX; sample inlet temperature: 280 ℃; carrier gas: helium with purity of 99.999% and flow rate of 3mL/min; sample injection mode: not split; chromatographic column flow rate: 1.0mL/min; heating program: the initial temperature is 60 ℃, kept for 1min, and is raised to 230 ℃ at a rate of 20 ℃/min and kept for 2min; sample injection amount: 11. Mu.L;
mass spectrometry: ionization mode: EI; ion source temperature: 230 ℃; four-stage bar temperature: 150 ℃, scanning range m/z:10-200 parts; SIM ion m/z: 58. 59, 103.
(4) Qualitative and quantitative analysis method
According to the analysis and test results of the instrument, the qualitative analysis is carried out on the tetraethylene glycol dimethyl ether through gas chromatography and mass spectrogram, the analysis and test curve is established according to the response values of the standard substances with different concentrations through the peak areas of the response values of mass spectrum fragment ions (m/z: 58, 59 and 103), and the quantitative analysis is carried out through an external standard method.
2. Detection result
(1) Peak out condition
The peak pattern of the results of the test of example 1 is shown in fig. 4, and it can be seen from fig. 4 that the peak pattern has good symmetry at a peak time of 7.8min and no impurity peak interference around the retention time.
(2) Linear range and detection limit
Further carrying out linear range determination and minimum detection limit test on the tetraethylene glycol dimethyl ether; the standard stock solution is diluted into a series of standard working solutions of 0.5mg/L, 1.0mg/L, 5.0mg/L, 10.0mg/L, 50.0mg/L and 100mg/L by acetonitrile step by step; drawing a standard working curve by taking mass concentration X (mg/L) as an abscissa and peak area Y as an ordinate; the linear equation and correlation coefficient of tetraethylene glycol dimethyl ether are shown in table 1;
Table 1: linear equation, correlation coefficient, detection limit and quantitative limit of tetraethylene glycol dimethyl ether
As can be seen from the data in Table 1, in the linear range of 0.5mg/L to 100mg/L, tetraethylene glycol dimethyl ether shows a good linear relationship, and the correlation coefficient is 0.9989; on this basis, the detection Limit (LOD) and the quantification Limit (LOQ) of the standard substance were determined with 3-fold and 10-fold signal-to-noise ratios (S/N), and the detection limit of the method was found to be 0.016mg/L and the quantification limit was found to be 0.055mg/L.
(3) Recovery and precision experiments
The recovery rate experiment is carried out by a blank matrix labeling experiment, a sample without tetraethylene glycol dimethyl ether is selected as a blank matrix, and 3 different labeling concentration levels (0.5 mg/L, 5mg/L and 100 mg/L) are set; each labeled level was tested 6 times in parallel (n=6), and precision experiments were performed; the test results are shown in table 2;
table 2: recovery rate and precision experimental result table
As can be seen from Table 2, under 3 standard adding levels, the recovery rate of the tetraglyme is 97.1% -101.2%, and the relative standard deviation of the recovery rate is less than 1.8%, which indicates that the accuracy of the test method is higher, and the test requirement can be met.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, and that those skilled in the art will understand that changes can be made to the technical solutions of the invention or equivalents thereof without departing from the spirit and scope of the technical solutions of the invention.
Claims (6)
1. A gas chromatography-mass spectrometry determination method of tetraethylene glycol dimethyl ether is characterized by comprising the following steps of:
(1) Extracting a sample to be detected in acetonitrile, and filtering to obtain filtrate;
(2) Carrying out gas chromatography-mass spectrometry detection on the filtrate obtained in the step (1);
Wherein, the measurement conditions of the gas chromatography-mass spectrometry are as follows:
Gas chromatography: chromatographic column: agilent DB-WAX; sample inlet temperature: 280 ℃; carrier gas: helium with purity of 99.999% and flow rate of 3mL/min; sample injection mode: not split; chromatographic column flow rate: 1.0-1.5mL/min; heating program: the initial temperature is 60 ℃, kept for 1-2min, and is raised to 230 ℃ at a speed of 15-20 ℃/min and kept for 2min; sample injection amount: 1 μl;
Mass spectrometry: ionization mode: EI; ion source temperature: 230 ℃; four-stage bar temperature: 150 ℃, scanning range m/z:10-200 parts; SIM ion m/z: 58. 59, 103;
The sample to be measured is water paint;
The extraction is ultrasonic extraction, the temperature of ultrasonic extraction is 40-60 ℃, the times of ultrasonic extraction are 1-2 times, and the time of single ultrasonic extraction is 10-90min.
2. The gas chromatography-mass spectrometry detection method according to claim 1, wherein the volume ratio of the mass of the sample to be detected to acetonitrile is 2.5g: (8-12) mL.
3. The gas chromatography-mass spectrometry detection method according to claim 1, wherein the temperature of the ultrasonic extraction is 60 ℃, the number of ultrasonic extraction is 2, and the time of single ultrasonic extraction is 10min.
4. The method according to claim 1, wherein the filtration is performed by a filter membrane having a pore size of 0.45 μm.
5. The method of claim 1, wherein the gas chromatography conditions are: chromatographic column: 30m 0.25mm,0.25 μm Agilent DB-WAX; chromatographic column flow rate: 1.0mL/min; heating program: the initial temperature was 60℃for 1min, and was raised to 230℃at a rate of 20℃per min and maintained for 2min.
6. Use of the gas chromatography-mass spectrometry detection method according to any one of claims 1 to 5 for detecting the content of tetraglyme in an aqueous coating.
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