CN114113389B - Liquid phase tandem mass spectrometer detection method for isopropylated triphenyl phosphate - Google Patents
Liquid phase tandem mass spectrometer detection method for isopropylated triphenyl phosphate Download PDFInfo
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000001514 detection method Methods 0.000 title claims abstract description 31
- 239000007791 liquid phase Substances 0.000 title claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000605 extraction Methods 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000004033 plastic Substances 0.000 claims abstract description 10
- 229920003023 plastic Polymers 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000006228 supernatant Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000002137 ultrasound extraction Methods 0.000 claims abstract description 8
- 239000010687 lubricating oil Substances 0.000 claims abstract description 7
- 238000002347 injection Methods 0.000 claims abstract description 6
- 239000007924 injection Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000012086 standard solution Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 150000002500 ions Chemical class 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000010828 elution Methods 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 10
- 239000011550 stock solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 238000004811 liquid chromatography Methods 0.000 claims description 6
- 239000012224 working solution Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 9
- -1 isopropyl triphenyl phosphate Chemical compound 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000000565 sealant Substances 0.000 abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000002372 labelling Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- LLMLGZUZTFMXSA-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobenzenethiol Chemical compound SC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl LLMLGZUZTFMXSA-UHFFFAOYSA-N 0.000 description 2
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007866 anti-wear additive Substances 0.000 description 2
- 231100000693 bioaccumulation Toxicity 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002085 persistent effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 239000013466 adhesive and sealant Substances 0.000 description 1
- 210000004100 adrenal gland Anatomy 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000000926 neurological effect Effects 0.000 description 1
- 210000001672 ovary Anatomy 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000001195 ultra high performance liquid chromatography Methods 0.000 description 1
- 210000001835 viscera Anatomy 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid 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
- G01N2030/062—Preparation extracting sample from raw material
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- Physics & Mathematics (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
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- General Health & Medical Sciences (AREA)
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- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
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Abstract
The application discloses a liquid phase tandem mass spectrometer detection method of isopropyl triphenyl phosphate, and belongs to the technical field of product detection. The detection method comprises the following steps: (1) preparing a standard solution; (2) sample preparation: adding an extraction solvent into a sample to be detected, performing ultrasonic extraction, and taking a supernatant; concentrating the obtained supernatant, fixing the volume by using methanol to obtain a concentrated solution, and filtering the concentrated solution to obtain a liquid to be detected; and (3) sample injection detection by using a liquid chromatograph-tandem mass spectrometer. The liquid phase tandem mass spectrometer detection method of the isopropylated triphenyl phosphate provided by the application has the advantages of strong interference resistance, low detection limit and quantitative limit, high precision and high recovery rate, and can meet the test requirements of the isopropylated triphenyl phosphate in electronic and electric product materials, lubricating oil, adhesives, sealants and plastics.
Description
Technical Field
The application belongs to the technical field of product detection, and particularly relates to a liquid phase tandem mass spectrometer detection method of isopropyl triphenyl phosphate.
Background
Isopropylated triphenyl phosphate, phenol, isopropylated Phosphate (3:1) (PIP 3:1) is used as a plasticizer, flame retardant, antiwear additive. Or compression resistant additives and plastic articles for use in hydraulic fluids, lubricating oils and greases, various industrial coatings, adhesives, sealants. As a chemical that can perform multiple functions at the same time, it has several unique uses sometimes under extreme conditions. In lubricating oils, PIP (3:1) is a flame retardant, an antiwear additive, an anti-compression additive, or some combination of the three. PIP (3:1) is a plasticizer and flame retardant in adhesives and sealants. PIP (3:1) can also be added to paints, coatings and plastic components, where it is a plasticizer or flame retardant additive.
PIP (3:1) was found to be toxic to aquatic plants, aquatic invertebrates, sediment invertebrates and fish. Potential reproductive and developmental effects, neurological effects and effects on internal organs, particularly adrenal glands, liver, ovaries and mammalian hearts. Five requirements for controlling persistent, bioaccumulation and toxic (PBT) substances such as isopropylated triphenyl phosphate are issued by the U.S. environmental protection agency (US EPA) in the Federal publication at 1/6 of 2021, however, the current research on isopropylated triphenyl phosphate is still focused on the fields of synthesis and application, and the detection of the content of the isopropylated triphenyl phosphate in products is rarely reported. It can be seen that it is necessary to establish a suitable method for determining the content of isopropylated triphenyl phosphate in the product.
Chinese patent application CN202110467556.1 discloses a method for rapidly determining the content of five persistent bioaccumulation toxic substances in consumer products, comprising the steps of: step a, sample preparation: a clean and pollution-free sample clamp is used for clamping a target sample, the target sample is cut into blocks or crushed by a crusher, and the samples are uniformly mixed to obtain a sample to be detected, wherein the sample to be detected is in a block shape or a particle shape; step b, extraction: weighing a certain mass of the sample to be detected, placing the sample into a reaction tube, measuring toluene, adding the toluene into the reaction tube, placing the reaction tube into an ultrasonic generator, performing ultrasonic extraction under a certain condition, taking supernatant to obtain a first sample liquid, and filtering the first sample liquid to obtain the sample liquid to be detected; step c, gas chromatography-mass spectrometry combined detection; and d, calculating the contents of five substances, namely 2,4, 6-tri (tertiary butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachloroprene in the sample liquid to be detected, and further obtaining the contents of five substances, namely 2,4, 6-tri (tertiary butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachloroprene in the target sample. The gas chromatograph is combined with mass spectrum, but the substances detectable by the gas chromatograph are volatile substances, so that the method is more limited and has larger experimental error. Compared with the method, the method can effectively detect the residues of the isopropylated triphenyl phosphate in different materials by using the liquid chromatography-tandem mass spectrometry, and has the advantages of strong anti-interference performance, low detection limit and quantitative limit and small error.
At present, few detection methods are available for the analysis of the residues of the isopropylated triphenyl phosphate in the electronic and electric products, and therefore, the application provides a liquid phase tandem mass spectrometer detection method for the isopropylated triphenyl phosphate, which solves the problem that the prior art cannot rapidly and accurately detect the isopropylated triphenyl phosphate in a sample.
Disclosure of Invention
The application aims to provide a liquid phase tandem mass spectrometer detection method of isopropylated triphenyl phosphate, which has the advantages of strong anti-interference performance, low detection limit and quantitative limit, high precision and high recovery rate, and can meet the test requirements of isopropylated triphenyl phosphate in lubricating oil, adhesive, sealant and plastics.
In order to achieve the above object, the present application has the following technical scheme:
in one aspect, the application provides a liquid phase tandem mass spectrometer detection method of isopropylated triphenyl phosphate, comprising the following steps:
(1) Preparing a standard solution;
(2) Sample preparation: adding an extraction solvent into a sample to be detected, performing ultrasonic extraction, and taking a supernatant; concentrating the obtained supernatant, fixing the volume by using methanol to obtain a concentrated solution, and filtering the concentrated solution to obtain a liquid to be detected;
(3) And (3) detecting by using a liquid chromatography tandem mass spectrometer.
Preferably, in step (1), the standard solution is prepared according to the following steps:
accurately weighing an isopropylated triphenyl phosphate standard substance, dissolving the standard substance with methanol, and fixing the volume to obtain a standard substance stock solution; the standard stock solution was diluted stepwise with methanol to give 5. Mu.g/L, 10. Mu.g/L, 50. Mu.g/L, 100. Mu.g/L, 200. Mu.g/L of a series of standard working solutions.
Preferably, in the step (2), the size of the sample to be measured is not more than 2mm×2mm. For the samples with larger sizes, the samples can be processed by shearing, grinding, crushing and the like, so that the sizes of the samples are not more than 2mm multiplied by 2mm.
Preferably, in the step (2), the extraction solvent is at least one selected from toluene, dichloromethane, methanol, acetonitrile, a mixed solution of n-hexane and acetone, and more preferably toluene. Toluene is preferred as the extraction solvent because it has an extraction efficiency of 85% or more for various types of samples, while the other extraction solvent is less than 85% in part/whole.
Preferably, in the step (2), the mass-volume ratio of the sample to be tested and the extraction solvent is 1:8-15 (g: mL), and more preferably 1:10 (g: mL).
Preferably, in the step (2), the temperature of the ultrasonic extraction is 50-70 ℃ and the time is 55-80 min; further preferably, the temperature of the ultrasonic extraction is 60 ℃ and the time is 60min.
Preferably, in the step (2), the concentration is performed by a common concentration method such as a rotary evaporator, and the concentration is performed until the concentration is near dryness.
In the step (2), the filtration may be performed in a conventional manner, and as a specific embodiment of the present application, a 0.22 μm filter membrane is selected.
As a preferred embodiment of the present application, the step (2) specifically comprises:
taking a sample with the size not larger than 2mm multiplied by 2mm, accurately weighing 1g of the sample, accurately weighing to 0.1mg, putting the sample into a sample bottle, adding 10mL of toluene into the sample bottle, screwing the bottle cap, putting the sample bottle into an ultrasonic cleaner, performing ultrasonic treatment at 60 ℃ for 60min, taking out the sample bottle, cooling, taking 5mL of supernatant, concentrating to near dryness by a rotary evaporator, fixing the volume to 1-2 mL by methanol, filtering a proper amount of concentrated solution by a 0.22 mu m filter membrane, and directly measuring. When the methanol is fixed to 1-2 mL, the detection limit is the lowest.
Preferably, in step (3), the conditions of the liquid chromatography are:
chromatographic column: PFP or C18 chromatographic column;
sample injection amount: 1.8-2 mu L;
column temperature: 35-45 ℃;
mobile phase: water (a) and acetonitrile (B);
flow rate: 0.18-0.22 mL/min,
elution mode: gradient elution.
Further preferably, in step (3), the conditions of the liquid chromatography are:
chromatographic column: poroshell 120PFP (2.1 x 100mm,2.7 μm);
sample injection amount: 1 μl;
column temperature: 40 ℃;
mobile phase: water (a) and acetonitrile (B);
flow rate: the concentration of the solution is 0.2mL/min,
elution mode: gradient elution, initial ratio a: b=40%: 60%; within 0-3 min, the ratio of A to B is gradually changed to 10 percent to 90 percent, and the time is kept for 1min; and gradually recovering A and B to 40 percent and 60 percent within 4 to 4.5 minutes, and keeping for 2 minutes.
Preferably, the mass spectrometry conditions are: ion source: AJS-ESI, nozzle pressure: 45psi, sheath air temperature: 330 ℃, sheath gas flow rate: 11L/min, atomizing gas flow rate: 5L/min, atomizer temperature: capillary voltage at 330 ℃): 3500V; MRM parameters: quantitative ion: parent ions 453, child ions 369.2, collision energy 20, qualitative ions: parent ion 453, child ion 327.2, collision energy 30.
On the other hand, the application also provides application of the detection method in detecting isopropylated triphenyl phosphate in materials, lubricating oil, adhesives, sealants and plastics of electronic and electric products.
The beneficial effects of the application are as follows:
(1) The application provides an ultra-high performance liquid chromatography tandem mass spectrometry detection method of isopropyl triphenyl phosphate, which meets the test requirements of isopropyl triphenyl phosphate in lubricating oil, adhesive, sealant and plastics;
(2) In the method of the application, the isopropyl triphenyl phosphate can obtain symmetrical chromatographic separation peaks in 3.7 min. Compared with other extraction solvents, toluene is used as the extraction solvent, and when methanol is used for concentration and volume fixing, the interference of the matrix is small, and the separation effect is optimal.
(3) The analysis test method has low detection limit, good precision, high sample labeling recovery rate, and good linear relation (r) of target compounds in the range of 5-200 mug/L 2 >0.995 A) is provided; the detection limit and the quantitative limit are both low, the detection limit is 0.013 mug/L, and the quantitative limit is 0.042 mug/L; the relative standard deviation is less than 10%; the sample standard recovery rate is 86-101%.
Drawings
FIG. 1 is a graph of isopropylated triphenyl phosphate under optimized conditions;
FIG. 2 is a graph of isopropylated triphenyl phosphate under mobile phase water (A) and methanol (B);
FIG. 3 is a graph of isopropylated triphenyl phosphate under ZORBAX Eclipse XDB-C18 column conditions;
FIG. 4 is a graph of the isopropylated triphenyl phosphate under the elution conditions of example 2.3;
FIG. 5 is a graph showing the effect of different extraction solvents on extraction efficiency;
FIG. 6 is a graph showing the effect of different extraction temperatures on extraction efficiency;
FIG. 7 is a graph showing the effect of different extraction times on extraction efficiency.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the application and are not intended to limit the application in any way. The following is merely exemplary of the scope of the application as claimed and many variations and modifications of the application will be apparent to those skilled in the art in light of the disclosure, which are intended to be within the scope of the application as claimed.
The application is further illustrated by means of the following specific examples. The various chemical reagents used in the examples of the present application were obtained by conventional commercial means unless otherwise specified.
Example 1
1.1 preparation of Standard working solution
(1) Preparing standard stock solution: accurately weighing 10mg (accurate to 0.1 mg) of standard substance, dissolving with methanol, and fixing the volume to a 10mL volumetric flask to obtain 1000mg/L stock solution of the standard substance, and storing in a refrigerator at 4 ℃ in a dark place.
(2) Preparing a standard working solution: the standard stock solution was diluted stepwise with methanol to give 5. Mu.g/L, 10. Mu.g/L, 50. Mu.g/L, 100. Mu.g/L, 200. Mu.g/L of a series of standard working solutions.
1.2 Instrument operating conditions
Liquid chromatography conditions:
chromatographic column: poroshell 120PFP (2.1 x 100mm,2.7 μm);
sample injection amount: 1 μl;
column temperature: 40 ℃;
mobile phase: water (a) and acetonitrile (B);
flow rate: 0.2mL/min;
elution mode: gradient elution, initial ratio a: b=40%: 60%; within 0-3 min, the ratio of A to B is gradually changed to 10 percent to 90 percent, and the time is kept for 1min; and gradually recovering A and B to 40 percent and 60 percent within 4 to 4.5 minutes, and keeping for 2 minutes.
Mass spectrometry conditions:
ion source: AJS-ESI, nozzle pressure: 45psi, sheath air temperature: 330 ℃, sheath gas flow rate: 11L/min, atomizing gas flow rate: 5L/min, atomizer temperature: capillary voltage at 330 ℃): 3500V; MRM parameters: quantitative ion: parent ions 453, child ions 369.2, collision energy 20, qualitative ions: parent ion 453, child ion 327.2, collision energy 30.
1.3 sample preparation
Plastic samples were taken, sheared/ground, and no greater than 2mm x 2mm in size. 1g of a sample (accurate to 0.1 mg) was weighed accurately into a sample bottle, to which 10mL of toluene was added. After the bottle cap is screwed, the sample bottle is put into an ultrasonic cleaner and is subjected to ultrasonic (60+/-5) min at 60 ℃. Taking out the sample bottle, cooling, taking 5mL of supernatant, concentrating to be nearly dry (0.05-0.1 mL) by using a rotary evaporator, fixing the volume to 1.5mL by using methanol, filtering a proper amount of concentrated solution by using a 0.22 mu m filter membrane, and directly measuring. FIG. 1 is a liquid chromatogram of isopropylated triphenyl phosphate under this condition, wherein the isopropylated triphenyl phosphate shows a peak at 3.67min, the chromatographic peak shape of the compound is sharp and symmetrical, and no impurity peak interference exists near the retention time.
1.4 Linear equation and detection Limit
The standard stock solution was serially diluted with toluene to a series of standard working solutions of 5. Mu.g/L, 10. Mu.g/L, 20. Mu.g/L, 50. Mu.g/L, 100. Mu.g/L, 200. Mu.g/L. And drawing a standard working curve by taking the mass concentration X (mg/L) as an abscissa and the peak area Y as an ordinate. The linear equation and the correlation coefficient of the obtained substance to be measured are shown in the following table.
TABLE 1 Linear equation, correlation coefficient, detection limit and quantitative limit of isopropylated triphenyl phosphate
As can be seen from the data in the table, the isopropylated triphenyl phosphate exhibits a good linear relationship in the linear range of 5 mug/L to 200 mug/L, and the correlation coefficient is 0.9998. 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 0.013. Mu.g/L, and the quantification limit was 0.042. Mu.g/L.
1.5 recovery and precision
The recovery rate experiment is carried out by a blank matrix labeling experiment, a sample without isopropylated triphenyl phosphate to be detected is selected as the blank matrix, and 3 different labeling concentration levels (5 mug/L, 50 mug/L and 200 mug/L) are set. Each labeled level was tested 3 times in parallel (n=3) and precision experiments were performed.
Under 3 standard adding levels, the standard adding recovery rate of the isopropyl triphenyl phosphate is 91% -101.2%, and the relative standard deviation of the recovery rate is not more than 10%, which indicates that the test method has higher accuracy and can meet the test requirement.
Example 2 influence of experimental conditions
2.1 different mobile phases
Compared to example 1, the mobile phase was modified as: water (a) and methanol (B), the remaining conditions being unchanged.
The results show that when water (A) and methanol (B) are selected as mobile phases, the isopropylated triphenyl phosphate has a late peak time and a wider peak width, as shown in figure 2; when water (A) and acetonitrile (B) are selected as mobile phases, the peak shape of the substance to be detected is symmetrical, the peak width is narrow, the response is high, and no impurity peak interference exists near the retention time, so that water-acetonitrile is selected as the mobile phase.
2.2 different chromatographic columns
In comparison with example 1, the remaining conditions were unchanged when a ZORBAX Eclipse XDB-C18 chromatographic column was used.
The results show that the reaction is lower by changing the chromatographic column into a ZORBAX Eclipse XDB-C18 chromatographic column, and the peak type is asymmetric, as shown in figure 3; and by using a poroshall 120PFP chromatographic column, the isopropylated triphenyl phosphate has high response, is not easily interfered by a matrix and has symmetrical peak type. Thus, the assay was finally selected using a Poroshell 120PFP column.
2.3 different elution conditions
In comparison with example 1, the elution mode is: within 0-1 min, the proportion of acetonitrile is 50%; gradually increasing from 50% to 80% within 1-2 min, and maintaining for 2min; the proportion gradually decreases from 80% to 50% within 4-5 min, and the time period is kept for 3min. Under this elution condition, the isopropylated triphenyl phosphate chromatographic peak is disturbed by the sample matrix and the retention time is unstable, as shown in fig. 4.
2.4 different extraction solvents
Four representative materials of electronic and electric products are selected: plastic, wire skin, foam and epoxy resin, then toluene, methylene dichloride, methanol, acetonitrile and mixed solution (n-hexane: acetone=1:1) are respectively selected as extraction solvents, and the extraction efficiency of the extraction solvents on isopropylated triphenyl phosphate in different samples is examined, as shown in fig. 5. The results show that in five different extraction solvents, the extraction efficiency of dichloromethane in plastics and wire barks is highest, but the pertinence is stronger, and the extraction efficiency is lower in terms of foam and epoxy resin; methanol and acetonitrile have relatively strong selectivity; toluene and mixed solution (n-hexane: acetone=1:1) have good applicability, and the comprehensive extraction efficiency can reach more than 85% only for each sample. The extraction efficiency of the four solvents of dichloromethane, methanol, acetonitrile and mixed solution (n-hexane: acetone=1:1) to the substances to be tested is partially/wholly lower than 85%, and the test requirements cannot be met. Therefore, toluene was found to have the best detection effect as an extraction solvent.
2.5 different extraction conditions
In order to study the influence of the extraction temperature and the extraction time on the test result, single comparison is carried out in the experiment, and the results are shown in fig. 6 and 7. The extraction temperature is respectively 40 ℃ and 60 ℃, the extraction time is respectively 30min, 60min and 90min, and the comparison test result shows that the recovery rate can reach more than 85% when the ultrasonic temperature is 60 ℃. After the ultrasonic time reaches 60min, the maximum extraction efficiency can be basically achieved. Taking practical factors into consideration, ultrasonic treatment at 60 ℃ for 60min is selected as the optimal extraction condition.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.
Claims (9)
1. The liquid phase tandem mass spectrometer detection method of the isopropylated triphenyl phosphate is characterized by comprising the following steps of:
(1) Preparing a standard solution;
(2) Sample preparation: adding an extraction solvent into a sample to be detected, performing ultrasonic extraction, and taking a supernatant; concentrating the obtained supernatant, fixing the volume by using methanol to obtain a concentrated solution, and filtering the concentrated solution to obtain a liquid to be detected;
(3) Detecting by using a liquid chromatograph tandem mass spectrometer;
wherein the extraction solvent in step (2) is selected from toluene;
the sample to be tested in the step (2) is selected from electronic and electric product materials, lubricating oil and plastics;
the conditions of the liquid chromatography in step (3) are:
chromatographic column: poroshell 120pfp,2.1 x 100mm,2.7 μm;
mobile phase: water a and acetonitrile B;
sample injection amount: 1.8 to 1.2 mu L;
column temperature: 35-45 ℃;
flow rate: 0.18-0.22 mL/min;
elution mode: gradient elution, initial ratio a: b=40%: 60%; within 0-3 min, the ratio of A to B is gradually changed to 10 percent to 90 percent, and the time is kept for 1min; gradually recovering A and B to 40 percent and 60 percent within 4 to 4.5 minutes, and keeping for 2 minutes;
in step (3), the mass spectrometry conditions are: ion source: AJS-ESI, nozzle pressure: 45psi, sheath air temperature: 330 ℃, sheath gas flow rate: 11L/min, atomizing gas flow rate: 5L/min, atomizer temperature: capillary voltage at 330 ℃): 3500V; MRM parameters: quantitative ion: parent ions 453, child ions 369.2, collision energy 20, qualitative ions: parent ion 453, child ion 327.2, collision energy 30.
2. The method according to claim 1, wherein in step (1), the standard solution is prepared by:
accurately weighing an isopropylated triphenyl phosphate standard substance, dissolving the standard substance with methanol, and fixing the volume to obtain a standard substance stock solution; the standard stock solution was diluted stepwise with methanol to give 5. Mu.g/L, 10. Mu.g/L, 50. Mu.g/L, 100. Mu.g/L, 200. Mu.g/L of a series of standard working solutions.
3. The method according to claim 1, wherein in the step (2), the size of the sample to be measured is not more than 2mm x 2mm.
4. The method according to claim 1, wherein in the step (2), the mass-to-volume ratio of the sample to be measured to the extraction solvent is 1 g:8-15 mL.
5. The method according to claim 4, wherein the mass-to-volume ratio of the sample to be tested and the extraction solvent is 1 g/10 mL.
6. The method according to claim 1, wherein in the step (2), the ultrasonic extraction is performed at a temperature of 50 to 70 ℃ for 55 to 80 minutes.
7. The method according to claim 6, wherein the ultrasonic extraction is performed at a temperature of 60℃for a period of 60 minutes.
8. The method according to claim 1, wherein the step (2) is specifically:
taking a sample with the size not larger than 2mm multiplied by 2mm, accurately weighing 1g of the sample to 0.1mg, putting the sample into a sample bottle, adding 10mL of toluene into the sample bottle, screwing up a bottle cap, putting the sample bottle into an ultrasonic cleaner, performing ultrasonic treatment at 60 ℃ for 60min, taking out the sample bottle, cooling, taking 5mL of supernatant, concentrating to near dryness by a rotary evaporator, fixing the volume to 1-2 mL by methanol, filtering a proper amount of concentrated solution by a 0.22 mu m filter membrane, and directly measuring; when the methanol is fixed to 1-2 mL, the detection limit is the lowest.
9. The method according to claim 1, wherein in the step (3), the conditions of the liquid chromatography are:
sample injection amount: 1 μl;
column temperature: 40 ℃;
flow rate: 0.2mL/min.
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| JPH11302474A (en) * | 1998-02-23 | 1999-11-02 | Idemitsu Petrochem Co Ltd | Propylene based resin, and film and laminate using the same |
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| JPH11302474A (en) * | 1998-02-23 | 1999-11-02 | Idemitsu Petrochem Co Ltd | Propylene based resin, and film and laminate using the same |
| CN112986416A (en) * | 2021-02-03 | 2021-06-18 | 暨南大学 | Multi-component large-flux detection method for plastic additive in atmospheric particulates |
| CN113219091A (en) * | 2021-04-28 | 2021-08-06 | 广东省中鼎检测技术有限公司 | Detection method for rapidly determining content of five persistent biological accumulated toxic substances in consumer product |
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