CN113063877A - Method for detecting solvent residue in cigarette bead blasting by headspace sample introduction-gas chromatography-mass spectrometry - Google Patents
Method for detecting solvent residue in cigarette bead blasting by headspace sample introduction-gas chromatography-mass spectrometry Download PDFInfo
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- 239000002904 solvent Substances 0.000 title claims abstract description 73
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- 239000011324 bead Substances 0.000 title claims abstract description 33
- 238000005422 blasting Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 title claims abstract description 19
- 238000001514 detection method Methods 0.000 claims abstract description 40
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012086 standard solution Substances 0.000 claims abstract description 14
- 239000001087 glyceryl triacetate Substances 0.000 claims abstract description 11
- 235000013773 glyceryl triacetate Nutrition 0.000 claims abstract description 11
- 229960002622 triacetin Drugs 0.000 claims abstract description 11
- 239000012224 working solution Substances 0.000 claims abstract description 9
- 238000004898 kneading Methods 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 16
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- 150000002500 ions Chemical class 0.000 claims description 10
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 7
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 7
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 7
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 7
- 229940093475 2-ethoxyethanol Drugs 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229940078552 o-xylene Drugs 0.000 claims description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 5
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 5
- 229940011051 isopropyl acetate Drugs 0.000 claims description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010813 internal standard method Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 5
- 239000011550 stock solution Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 6
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 4
- 230000000391 smoking effect Effects 0.000 description 4
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011067 equilibration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- 238000011002 quantification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JKOSHCYVZPCHSJ-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1.CC1=CC=CC=C1 JKOSHCYVZPCHSJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- JMVIPXWCEHBYAH-UHFFFAOYSA-N cyclohexanone;ethyl acetate Chemical compound CCOC(C)=O.O=C1CCCCC1 JMVIPXWCEHBYAH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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- 238000004949 mass spectrometry Methods 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- ZQBVUULQVWCGDQ-UHFFFAOYSA-N propan-1-ol;propan-2-ol Chemical compound CCCO.CC(C)O ZQBVUULQVWCGDQ-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- 239000000779 smoke Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- MECFLMNXIXDIOF-UHFFFAOYSA-L zinc;dibutoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CCCCOP([S-])(=S)OCCCC.CCCCOP([S-])(=S)OCCCC MECFLMNXIXDIOF-UHFFFAOYSA-L 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
-
- 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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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for detecting solvent residues in cigarette blasting beads by headspace sample injection-gas chromatography-mass spectrometry, which comprises the following steps: placing the cigarette blasting beads of the sample to be detected in paper, kneading the paper, adding the paper into a headspace bottle, and adding glyceryl triacetate and an internal standard solution into the headspace bottle to perform gas chromatography-mass spectrometry combined detection to obtain detection values of various solvent residues of the sample to be detected; adding paper base paper into a headspace bottle, sequentially adding a series of standard working solutions and internal standard solutions mixed with various solvent residues into the base paper for detection to obtain detection values of various solvent residues with different concentrations, and establishing a standard curve according to the detection values. The method for detecting the solvent residue in the cigarette blasting beads by the headspace sample injection-gas chromatography-mass spectrometry has the advantages of simple detection process, accurate detection result and low detection cost.
Description
Technical Field
The invention relates to the technical field of detection, in particular to a method for detecting solvent residues in cigarette blasting beads by combining headspace sample introduction, gas chromatography and mass spectrometry.
Background
The cigarette blasting bead is a spherical capsule made of film-forming material, and is formed from a layer of rubber shell and liquid content wrapped by said shell, and some products are coated with coating film, and mainly used in cigarette filter stick. The cigarette can be broken when being smoked, the wrapped functional substances are released, the smoking quality of the cigarette is improved, the fragrance is enhanced, or the moisture degree of smoke is increased, the smoking taste of the cigarette is enriched, and the effects of increasing aroma, keeping moisture, reducing harm and the like in the smoking process are realized. The solvent residue not only can influence the smoking safety and quality of cigarettes, but also can cause certain harm to the environment, particularly, part of the solvent (such as benzene solvents) can cause the harm of carcinogenesis, teratogenesis, mutation and the like to human bodies, so that the accurate determination of the solvent residue in the bead blasting is a key technology for bead blasting safety evaluation.
At present, in the detection process of the organic solvent residue in the cigarette blasting bead, no method for detecting the organic solvent residue in the cigarette blasting bead with stronger pertinence and more accurate quantification exists, so that the technical problem to be solved in the technical field of chemical analysis and test is how to overcome the defects of the prior art.
Disclosure of Invention
Therefore, the invention provides a method for detecting solvent residues in cigarette blasting beads by using headspace sample injection-gas chromatography-mass spectrometry.
In order to achieve the above purpose, the invention provides the following technical scheme:
the embodiment of the invention provides a method for detecting solvent residues in cigarette blasting beads by headspace sampling-gas chromatography-mass spectrometry, which comprises the following steps:
placing the cigarette blasting beads of the sample to be detected in paper, kneading the paper, adding the paper into a headspace bottle, and adding glyceryl triacetate and an internal standard solution into the headspace bottle to perform gas chromatography-mass spectrometry combined detection to obtain detection values of various solvent residues of the sample to be detected;
adding paper base paper into a headspace bottle, sequentially adding a series of standard working solutions and internal standard solutions mixed with various solvent residues into the base paper for detection to obtain detection values of various solvent residues with different concentrations, and establishing a standard curve according to the detection values;
calculating and calculating C according to each solvent residue detection value of each sample to be detected and each corresponding solvent residue standard curveiAnd Ci0The solvent residue is calculated according to the formula (1):
wherein X is the residual quantity of the solvent in the sample to be detected, and the unit is milligram per kilogram; ciThe concentration of the solvent residue in the sample to be tested is obtained from the standard working curve, and the unit is milligram per liter; ci0Is the concentration of solvent residue in milligrams per liter in the blank from the standard working curve; v is the volume of the standard working solution removed in milliliters; and m is the mass of the sample to be measured and has the unit of gram.
In one embodiment of the invention, the individual solvent residues are methanol, ethanol, isopropanol, acetone, n-propanol, butanone, ethyl acetate, isopropyl acetate, n-butanol, benzene, 1-methoxy-2-propanol, n-propyl acetate, 2-ethoxyethanol, 4-methyl-2-pentanone, 1-ethoxy-2-propanol, toluene, n-butyl acetate, ethylbenzene, m, p-xylene, o-xylene, styrene, 2-ethoxyethyl acetate, cyclohexanone, dimethyl succinate, dimethyl glutarate, dimethyl adipate.
In one embodiment of the present invention, the gas chromatograph detection conditions are: a capillary column special for VOC, wherein carrier gas is helium, and the flow rate is 2.0mL/min in a constant-current mode; the temperature of a sample inlet is 180 ℃; the split ratio is 20: 1; temperature programming: keeping at 40 deg.C for 2min, heating to 200 deg.C at 4 deg.C/min, and keeping for 10 min.
In one embodiment of the present invention, the mass spectrometer detection conditions are: the temperature of the auxiliary interface is 220 ℃; the ionization mode is an electron bombardment source, the temperature of the ion source is 280 ℃, the ionization energy is 70eV, the temperature of the quadrupole rod is 150 ℃, the full-scanning monitoring mode is adopted, and the scanning range is 29 amu-350 amu.
In one embodiment of the invention, the mass of the test sample cigarette bead is 0.1 g.
In one embodiment of the present invention, the calculation method of each solvent residue is an internal standard method.
The principle of the detection method of the embodiment of the invention is as follows: when the solvent residue in the sample to be tested reaches the equilibrium between gas phase and matrix (liquid phase or solid phase) in a closed container at a certain temperature, introducing the gas phase part into a gas chromatography/mass spectrometer for separation and identification, and measuring the solvent residue in the sample after matrix correction.
The invention has the following advantages:
the method for detecting the solvent residue in the cigarette blasting beads by the headspace sample injection-gas chromatography-mass spectrometry has the advantages of simple detection process, accurate detection result and low detection cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions that the present invention can be implemented, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the effects and the achievable by the present invention, should still fall within the range that the technical contents disclosed in the present invention can cover.
Fig. 1 is a standard total ion chromatogram of 26 solvent residues obtained by the method for detecting solvent residues in cigarette blasting beads by headspace sampling-gas chromatography-mass spectrometry provided by the embodiment of the invention, wherein the solvent residue component to be detected: 1-methanol; 2-ethanol; 3-isopropanol; 4-propanone; 5-n-propanol; 6-butanone; 7-ethyl acetate; isopropyl 8-acetate; 9-n-butanol; 10-benzene; 11-1-methoxy-2-propanol; 12-n-propyl acetate; 13-2-ethoxyethanol; 14-4-methyl-2-pentanone; 15-1-ethoxy-2-propanol; 16-toluene; 17-n-butyl acetate; 18-ethylbenzene; 19-m, p-xylene; 20-o-xylene; 21-styrene; 22-2-ethoxyethyl acetate; 23-cyclohexanone; 24-succinic acid dimethyl ester; 25-glutaric acid dimethyl ester; 26-adipic acid dimethyl ester; internal standard: IS 1-dichloromethane; IS 2-fluorobenzene; IS 3-diethylene glycol dimethyl ether;
fig. 2 is a chromatogram of a typical cigarette bead blasting sample detected by the method for detecting solvent residue in cigarette bead blasting by headspace sampling-gas chromatography-mass spectrometry provided by the embodiment of the invention, wherein the solvent residue component to be detected is as follows: 5-n-propanol; 16-toluene; 17-n-butyl acetate; 23-cyclohexanone; internal standard: IS 1-dichloromethane; IS 2-fluorobenzene; IS 3-diethylene glycol dimethyl ether.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The detection method is suitable for measuring the residual of 26 solvents listed in table 1 in the cigarette blasting beads. Table 1 shows the solvent residues and the corresponding detection and quantification limits for the process of the invention.
TABLE 1
Reagents and materials: except for special requirements, all the reagents are analytically pure.
Matrix correction agent: glyceryl triacetate.
Solvent residue standards, typical solvent residue standards: benzene; toluene; ethylbenzene; (o, m, p) xylene; styrene; methanol; ethanol; isopropyl alcohol; n-propanol; n-butanol; acetone; 4-methyl-2-pentanone; butanone; cyclohexanone; ethyl acetate; n-propyl acetate; n-butyl acetate; isopropyl acetate; 2-ethoxyethyl acetate; 1-methoxy-2-propanol; 1-ethoxy-2-propanol; 2-ethoxyethanol; dimethyl succinate; dimethyl glutarate; adipic acid dimethyl ester. Other solvent residue standards: determined by qualitative analysis of the popped bead sample.
Internal standard: dichloromethane (purity is more than or equal to 98%); fluorobenzene (purity is more than or equal to 98%); diethylene glycol dimethyl ether (purity is more than or equal to 98%);
preparing a standard solution, mixing a standard stock solution: and respectively weighing corresponding solvent residue standard samples according to the qualitative analysis result of the solvent residue in the detection sample, and dissolving the solvent residue standard samples in the glyceryl triacetate to prepare a mixed standard stock solution.
The typical solvent mixed standard stock solution recommends the preparation method: respectively and accurately weighing 1000mg of ethanol, n-propyl acetate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dimethyl succinate, dimethyl glutarate and dimethyl adipate, 15mg of benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene and styrene, 150mg of methanol, isopropanol, n-propanol, n-butanol, acetone, 4-methyl-2-pentanone, butanone, cyclohexanone, ethyl acetate, n-butyl acetate, isopropyl acetate, 2-ethoxyethyl acetate and 2-ethoxyethanol in a 100mL volumetric flask, respectively, accurately measuring the volume to 0.1mg, and preparing a mixed standard stock solution by using glyceryl triacetate to fix the volume. The concentration of ethanol, n-propyl acetate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dimethyl succinate, dimethyl glutarate and dimethyl adipate in the prepared mixed standard stock solution is 10mg/mL, the concentration of benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene and styrene is 0.15mg/mL, and the concentration of other substances is 1.5 mg/mL. The mixed standard stock solution is stored in a sealed and light-proof way at the temperature of-18 ℃ and the effective period is 6 months. And preparing standard stock solutions by other solvent residue standard samples according to actual conditions.
Mixing standard solutions: accurately transferring 0.5mL of mixed standard stock solution into a 10mL volumetric flask, and carrying out constant volume to a scale by using glyceryl triacetate to prepare a mixed standard solution. The concentration of ethanol, n-propyl acetate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dimethyl succinate, dimethyl glutarate and dimethyl adipate in the prepared mixed standard solution was 500. mu.g/mL, the concentration of benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene and styrene was 7.5. mu.g/mL, and the concentration of other substances was 75. mu.g/mL. The mixed standard stock solution is stored in a sealed and light-proof way at the temperature of-18 ℃ and the effective period is3 months.
And (3) accurately transferring the standard working solution into a 10mL volumetric flask by using 0.1mL, 0.2mL, 0.4mL, 0.8mL and 1mL of mixed standard solution, and metering the volume to a scale by using glyceryl triacetate to obtain a series of standard working solutions.
Internal standard stock solution (1mg/mL), accurately weighing 10.0mg (accurate to 0.1mg) of dichloromethane, fluorobenzene and diethylene glycol dimethyl ether in a 10mL volumetric flask, and fixing the volume to the scale by using glyceryl triacetate. The internal standard stock solution is stored in a sealed and light-proof way at the temperature of 18 ℃ below zero, and the effective period is 6 months.
And (3) accurately transferring 1mL of internal standard stock solution into a 100mL volumetric flask, and metering to the scale with glyceryl triacetate. The internal standard solution is stored in a sealed and lightproof way at the temperature of-18 ℃ and the validity period is 6 months. Table 2 shows the correspondence between the components to be measured and the internal standard.
TABLE 2
The instrument comprises the following steps: static headspace (G1888); a gas chromatograph (7890A); a mass spectrometer (5975C); typical solvent residue ion selection parameters are shown in figure 1.
An analytical balance, a sensory mass of 0.1 mg; 1000L of piston-type pipette; processing paper base paper for 2h at 105 ℃, and cutting into the size of 15.5cm multiplied by 10 cm;
example 1
The embodiment provides a method for detecting solvent residues in cigarette blasting beads by headspace sampling-gas chromatography-mass spectrometry, which comprises the following steps:
step one, preparation and detection of sample to be detected
Accurately weighing 0.1g (accurate to 0.1mg) of the exploded cigarette bead of the sample to be detected, placing the exploded cigarette bead of the sample to be detected in raw paper of paper with the thickness of 15cm multiplied by 10cm, rolling the raw paper, putting the crushed exploded cigarette bead of the sample to be detected and the whole raw paper into a headspace bottle, adding 1mL of substrate correction agent glyceryl triacetate and 100 mu L of internal standard solution into the headspace bottle, rapidly sealing, and performing machine-on detection to obtain the detection value of each solvent residue of the sample to be detected.
The specific detection conditions are as follows: static headspace device, 20 mL; sample loop, 3.0 mL; the sample equilibrium temperature, 100 ℃; sample loop temperature, 160 ℃; transmission line temperature, 180 ℃; sample equilibration time, 45.0 min; sample bottle pressurization pressure, 138 kPa; pressurizing for 0.20 min; aerating for 0.20 min; sample ring equilibration time, 0.05 min; sample injection time, 1.0 min.
The detection conditions of the gas chromatograph are as follows: a capillary column (VOCOL column or equivalent column) special for VOC, the specification is [60m (length) × 0.32mm (inner diameter) × 1.8 μm (film thickness) ]; carrier gas: helium (He), constant flow mode, flow 2.0 mL/min; sample inlet temperature: 180 ℃; the split ratio is as follows: 20: 1; temperature programming: keeping at 40 deg.C for 2min, heating to 200 deg.C at 4 deg.C/min, and keeping for 10 min.
The mass spectrometer detection conditions are as follows: auxiliary interface temperature: 220 ℃; an ionization mode: an electron impact source (EI); ion source temperature: 280 ℃; (ii) a Ionization energy: 70 eV; temperature of the quadrupole rods: 150 ℃; a full-scanning monitoring mode, wherein the scanning range is 29 amu-350 amu, and ions with higher specificity and response are selected as quantitative ions; and selecting other 1-2 fragment ions as auxiliary qualitative ions. Typical solvent residue ion selection parameters are shown in figure 1.
And (3) determining the samples to be tested according to the testing conditions of the instrument, and determining the samples to be tested twice in parallel by using retention time for qualitative determination and an internal standard method for quantitative determination.
Step two, manufacturing of standard curve
Filling cut 15cm x 10cm paper base paper into a headspace bottle, adding 1mL of corresponding standard working solution and 100 muL of internal standard solution into the base paper, measuring according to the above conditions of the instrument to obtain detection values of different concentrations of each solvent residue, drawing a standard curve according to the ratio of the concentration of each solvent to the area of the response peak and the area of the internal standard response peak, and obtaining a correlation coefficient R2Should not be less than 0.99. The concentration range of the standard curve can be adjusted properly if the concentration range of the sample is beyond the range of the standard curve.
Step three, calculating C according to the detection value of each solvent residue of the sample to be detected in the step one and the standard curve corresponding to each solvent residue in the step twoiAnd Ci0. As shown in table 3
TABLE 3
The calculation result, solvent residual quantity according to formula (1) is calculated:
in the formula: x is the residual quantity of solvent in the sample to be tested, and the unit is milligram per kilogram (mg/kg); ciThe concentration of the solvent residue in milligrams per liter (mg/L) in the sample to be tested is obtained from the standard working curve; ci0Is the concentration of solvent residue in milligrams per liter (mg/L) in the blank from the standard working curve; v is the volume of standard working solution removed in milliliters (mL); and m is the mass of the sample to be measured and has the unit of gram (g). The results are expressed as the average of two replicates to the nearest 0.1. mu.g/g, and the relative deviation between the two measurements should be less than 10%.
The results of the recovery and precision tests of the method of the present invention are shown in table 4.
TABLE 4
| Solvent residue | Average recovery (%) | Average RSD (%) |
| Methanol | 88.4 | 6.1 |
| Ethanol | 99.4 | 9.9 |
| Isopropanol (I-propanol) | 86.4 | 4.8 |
| Acetone (II) | 85.0 | 8.0 |
| N-propanol | 89.2 | 4.1 |
| Butanone | 92.1 | 4.2 |
| Ethyl acetate | 98.5 | 9.3 |
| Acetic acid isopropyl ester | 83.3 | 5.5 |
| N-butanol | 97.7 | 4.5 |
| Benzene and its derivatives | 95.3 | 3.7 |
| 1-methoxy-2-propanol | 93.9 | 2.1 |
| N-propyl acetate | 105.6 | 8.8 |
| 2-Ethoxyethanol | 97.5 | 4.3 |
| 4-methyl-2-pentanone | 92.8 | 4.0 |
| 1-ethoxy-2-propanol | 96.1 | 1.8 |
| Toluene | 96.6 | 2.1 |
| Acetic acid n-butyl ester | 92.1 | 3.3 |
| Ethylbenzene production | 98.9 | 1.8 |
| Meta, para-xylene | 97.4 | 1.8 |
| Ortho-xylene | 92.6 | 3.5 |
| Styrene (meth) acrylic acid ester | 95.4 | 1.7 |
| 2-Ethoxyethyl acetate | 93.9 | 4.7 |
| Cyclohexanone | 94.6 | 5.1 |
| Succinic acid dimethyl ester | 97.2 | 2.6 |
| Glutaric acid dimethyl ester | 96.1 | 5.3 |
| Adipic acid dimethyl ester | 87.5 | 5.8 |
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (6)
1. A headspace sample injection-gas chromatography-mass spectrometry combined method for detecting solvent residues in cigarette blasting beads is characterized by comprising the following steps:
placing the cigarette blasting beads of the sample to be detected in paper, kneading the paper, adding the paper into a headspace bottle, and adding glyceryl triacetate and an internal standard solution into the headspace bottle to perform gas chromatography-mass spectrometry combined detection to obtain detection values of various solvent residues of the sample to be detected;
adding paper base paper into a headspace bottle, sequentially adding a series of standard working solutions and internal standard solutions mixed with various solvent residues into the base paper for detection to obtain detection values of various solvent residues with different concentrations, and establishing a standard curve according to the detection values;
calculating and calculating C according to each solvent residue detection value of each sample to be detected and each corresponding solvent residue standard curveiAnd Ci0The solvent residue is calculated according to the formula (1):
wherein X is the residual quantity of the solvent in the sample to be detected, and the unit is milligram per kilogram; ciThe concentration of the solvent residue in the sample to be tested is obtained from the standard working curve, and the unit is milligram per liter; ci0Is the concentration of solvent residue in milligrams per liter in the blank from the standard working curve; v is the volume of the standard working solution removed in milliliters; and m is the mass of the sample to be measured and has the unit of gram.
2. The method for detecting the solvent residue in the cigarette blasting beads by the combination of headspace sampling-gas chromatography-mass spectrometry as claimed in claim 1,
the solvent residues are methanol, ethanol, isopropanol, acetone, n-propanol, butanone, ethyl acetate, isopropyl acetate, n-butanol, benzene, 1-methoxy-2-propanol, n-propyl acetate, 2-ethoxyethanol, 4-methyl-2-pentanone, 1-ethoxy-2-propanol, toluene, n-butyl acetate, ethylbenzene, m, p-xylene, o-xylene, styrene, 2-ethoxyethyl acetate, cyclohexanone, dimethyl succinate, dimethyl glutarate and dimethyl adipate.
3. The method for detecting the solvent residue in the cigarette blasting beads by the combination of headspace sampling-gas chromatography-mass spectrometry as claimed in claim 1,
the detection conditions of the gas chromatograph are as follows: a capillary column special for VOC, wherein carrier gas is helium, and the flow rate is 2.0mL/min in a constant-current mode; the temperature of a sample inlet is 180 ℃; the split ratio is 20: 1; temperature programming: keeping at 40 deg.C for 2min, heating to 200 deg.C at 4 deg.C/min, and keeping for 10 min.
4. The method for detecting the solvent residue in the cigarette blasting beads by the combination of headspace sampling-gas chromatography-mass spectrometry as claimed in claim 1,
the mass spectrometer detection conditions are as follows: the temperature of the auxiliary interface is 220 ℃; the ionization mode is an electron bombardment source, the temperature of the ion source is 280 ℃, the ionization energy is 70eV, the temperature of the quadrupole rod is 150 ℃, the full-scanning monitoring mode is adopted, and the scanning range is 29 amu-350 amu.
5. The method for detecting the solvent residue in the cigarette blasting beads by the combination of headspace sampling-gas chromatography-mass spectrometry as claimed in claim 1,
the mass of the cigarette bead to be tested is 0.1 g.
6. The method for detecting the solvent residue in the cigarette blasting beads by the combination of headspace sampling-gas chromatography-mass spectrometry as claimed in claim 1,
the calculation method of each solvent residue is an internal standard method.
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| CN115356417A (en) * | 2022-10-08 | 2022-11-18 | 山东海科创新研究院有限公司 | Method for detecting residual solvent in epoxy resin |
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