CN114113389A - Detection method of isopropylated triphenyl phosphate by liquid-phase tandem mass spectrometer - Google Patents
Detection method of isopropylated triphenyl phosphate by liquid-phase tandem mass spectrometer 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 43
- 238000001514 detection method Methods 0.000 title claims abstract description 39
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- 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
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant 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
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- 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
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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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- 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
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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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- G01N30/06—Preparation
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Abstract
The invention discloses a liquid phase tandem mass spectrometer detection method of isopropylated 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 supernatant; concentrating the obtained supernatant, diluting with methanol to constant volume to obtain concentrated solution, and filtering the concentrated solution to obtain solution to be detected; (3) and (3) detecting by using a liquid chromatography tandem mass spectrometer. The detection method of the liquid-phase tandem mass spectrometer of the isopropylated triphenyl phosphate provided by the invention has the advantages of strong anti-interference performance, low detection limit and quantification limit, high precision and high recovery rate, and can meet the test requirements of isopropylated triphenyl phosphate in electronic and electric product materials, lubricating oil, adhesives, sealants and plastics.
Description
Technical Field
The invention belongs to the technical field of product detection, and particularly relates to a liquid phase tandem mass spectrometer detection method of isopropylated triphenyl phosphate.
Background
Isopropylated triphenyl Phosphate, Phenol, isoproylated Phenol (3:1) (PIP 3:1), is used as a plasticizer, flame retardant, anti-wear additive. Or compression resistant additives and plastics for use in hydraulic fluids, lubricating oils and greases, various industrial coatings, adhesives, sealants. As a chemical that can perform multiple functions simultaneously, 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. In adhesives and sealants, PIP (3:1) is a plasticizer and flame retardant. PIP (3:1) may also be added to paints, coatings and plastic components where it is a plasticizer or flame retardant additive.
Studies have demonstrated that PIP (3:1) is toxic to aquatic plants, aquatic invertebrates, sediment invertebrates and fish. Potential reproductive and developmental effects, neurological effects and effects on internal organs, particularly the adrenal gland, liver, ovary and the mammalian heart. At 6 months 1/2021, the U.S. environmental protection agency (US EPA) issued in federal bulletin the management and control requirements of five substances with persistence, bioaccumulation and toxicity (PBT), such as isopropylated triphenyl phosphate, however, research on isopropylated triphenyl phosphate is still focused on the synthesis and application fields, and there are rare reports about the detection of its content in products. It can be seen that it is necessary to establish a suitable method for determining the amount of isopropylated triphenyl phosphate in the product.
Chinese patent application CN202110467556.1 discloses a detection method for rapidly determining the content of five persistent bioaccumulation toxic substances in consumer products, comprising the following steps: step a, sample preparation: taking a clean pollution-free sample clamp to clamp a target sample, cutting the target sample into blocks or crushing the target sample by using a crusher, and uniformly mixing to obtain a sample to be detected, wherein the sample to be detected is in a block shape or a granular shape; step b, extraction: weighing a certain mass of the sample to be detected, placing the sample to be detected in a reaction tube, weighing toluene, adding the toluene into the reaction tube, placing the reaction tube in an ultrasonic generator, performing ultrasonic extraction under certain conditions, taking supernatant to obtain first sample liquid, and filtering the first sample liquid to obtain sample liquid to be detected; step c, gas chromatography-mass spectrometry combined detection; and d, calculating the content of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene in the sample solution to be detected, and further obtaining the content of five substances, namely 2,4, 6-tri (tert-butyl) phenol, decabromodiphenyl ether, isopropylated triphenyl phosphate, pentachlorothiophenol and hexachlorobutadiene in the target sample. The gas chromatography-mass spectrometry is used, but substances detectable by the gas chromatography are only volatile substances, so that the limitation is large, and the experimental error is large. Compared with the prior art, the detection method has the advantages that the liquid chromatogram tandem mass spectrum is used, residues of isopropylated triphenyl phosphate in different materials can be effectively detected, the anti-interference performance is strong, the detection limit and the quantification limit are low, and the error is small.
At present, the detection method for analyzing the residue of isopropylated triphenyl phosphate in electronic and electric products is still few, and in view of the above, the application provides a detection method for a liquid-phase tandem mass spectrometer of isopropylated triphenyl phosphate, which solves the problem that the prior art cannot rapidly and accurately detect isopropylated triphenyl phosphate in a sample.
Disclosure of Invention
The invention aims to provide a liquid-phase tandem mass spectrometer detection method for isopropylated triphenyl phosphate, which has strong anti-interference performance, low detection limit and quantification limit, high precision and high recovery rate and can meet the test requirements of isopropylated triphenyl phosphate in lubricating oil, adhesives, sealants and plastics.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on one hand, the invention provides a detection method of a liquid phase tandem mass spectrometer of isopropylated triphenyl phosphate, which 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 supernatant; concentrating the obtained supernatant, diluting with methanol to constant volume to obtain concentrated solution, and filtering the concentrated solution to obtain solution 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 isopropylated triphenyl phosphate 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 obtain 5. mu.g/L, 10. mu.g/L, 50. mu.g/L, 100. mu.g/L, and 200. mu.g/L series of standard working solutions.
Preferably, in the step (2), the size of the sample to be measured is not more than 2mm × 2 mm. For samples with larger size, the sample can be processed by shearing, grinding, crushing and the like, so that the size of the sample is not more than 2mm multiplied by 2 mm.
Preferably, in the step (2), the extraction solvent is at least one selected from the group consisting of toluene, dichloromethane, methanol, acetonitrile, a mixed solution of n-hexane and acetone, and more preferably toluene. The extraction efficiency of toluene for various samples can reach more than 85%, and the extraction efficiency of other extraction solvents is lower than 85% in part/whole, so toluene is preferably used as the extraction solvent.
Preferably, in the step (2), the mass-to-volume ratio of the sample to be tested to 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 60 min.
Preferably, in the step (2), the concentration is performed by a conventional concentration method such as a rotary evaporator, and the concentration is performed to be near dry.
In the step (2), the filtration may be a common filtration mode, and as a specific embodiment of the present invention, a 0.22 μm filter membrane is selected for filtration.
As a preferred embodiment of the present application, step (2) is specifically:
taking a sample with the size of not more than 2mm multiplied by 2mm, accurately weighing 1g of sample, accurately weighing the sample to 0.1mg, placing the sample into a sample bottle, adding 10mL of methylbenzene into the sample bottle, screwing a bottle cap, placing the sample bottle into an ultrasonic cleaning instrument, performing ultrasonic treatment at 60 ℃ for 60min, taking out the sample bottle, cooling, taking 5mL of supernatant, concentrating the supernatant to be nearly dry by using a rotary evaporator, performing volume fixing to 1-2 mL by using methanol, filtering a proper amount of concentrated solution by using a 0.22 mu m filter membrane, and directly determining. When the volume of the methanol is constant to 1-2 mL, the detection limit is lowest.
Preferably, in the step (3), the conditions of the liquid chromatography are as follows:
a chromatographic column: PFP or C18 chromatography columns;
sample introduction amount: 1.8-2 mu L;
column temperature: 35-45 ℃;
mobile phase: water (a) and acetonitrile (B);
flow rate: 0.18 to 0.22mL/min,
and (3) an elution mode: gradient elution.
Further preferably, in the step (3), the conditions of the liquid chromatography are as follows:
a chromatographic column: poroshell 120PFP (2.1 x 100mm, 2.7 μm);
sample introduction amount: 1 mu L of the solution;
column temperature: 40 ℃;
mobile phase: water (a) and acetonitrile (B);
flow rate: 0.2mL/min of the reaction solution,
and (3) an elution mode: gradient elution, wherein the initial proportion A to B is 40 percent to 60 percent; within 0-3 min, gradually changing A: B to 10% and 90% and keeping for 1 min; within 4-4.5 min, the A: B gradually recovers to 40% and 60%, and the time is kept for 2 min.
Preferably, the mass spectrometry conditions are: an ion source: AJS-ESI, nozzle pressure: 45psi, sheath gas temperature: 330 ℃, sheath gas flow rate: 11L/min, atomizing gas flow rate: 5L/min, atomizer temperature: 330 ℃, capillary voltage: 3500V; MRM parameters: and (3) quantifying ions: parent ion 453, daughter ion 369.2, collision energy 20, qualitative ion: parent ion 453, child ion 327.2, collision energy 30.
On the other hand, the invention also provides the application of the detection method in detecting isopropylated triphenyl phosphate in materials, lubricating oil, adhesives, sealants and plastics of electronic and electric products.
The invention has the beneficial effects that:
(1) the invention provides an ultra-high performance liquid chromatography tandem mass spectrometry detection method of isopropylated triphenyl phosphate, which meets the test requirements of isopropylated triphenyl phosphate in lubricating oil, adhesives, sealants and plastics;
(2) in the method, the isopropylated triphenyl phosphate can obtain a symmetrical chromatographic separation peak within 3.7 min. Compared with other extraction solvents, the toluene is used as the extraction solvent, and when methanol is used for concentration and volume fixing, the matrix interference is small, and the separation effect is optimal.
(3) The analytical test method has the advantages of low detection limit, good precision, high sample standard addition recovery rate and good linear relation (r) of the target compound in the range of 5-200 mu g/L2>0.995); 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 recovery rate of the sample by adding the standard is 86-101%.
Drawings
FIG. 1 is a spectrum of isopropylated triphenyl phosphate under optimized conditions;
FIG. 2 is a diagram of mobile phase water (A) and methanol (B) conditions for isopropylated triphenyl phosphate;
FIG. 3 is a spectrum 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 of 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 are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. The following is merely an exemplary illustration of the scope of the invention as claimed, and various changes and modifications of the invention of the present application may be made by those skilled in the art based on the disclosure, which also fall within the scope of the invention as claimed.
The present invention will be further described below by way of specific examples. The various chemicals used in the examples of the present invention were obtained by conventional commercial routes unless otherwise specified.
Example 1
1.1 preparation of Standard working solutions
(1) Preparing a standard stock solution: accurately weighing 10mg (accurate to 0.1mg) of standard substance, dissolving with methanol, and diluting to a volume of 10mL volumetric flask to obtain 1000mg/L stock solution of standard substance, and storing in a refrigerator at 4 deg.C in dark place.
(2) Preparing a standard working solution: the standard stock solution was diluted stepwise with methanol to obtain 5. mu.g/L, 10. mu.g/L, 50. mu.g/L, 100. mu.g/L, and 200. mu.g/L series of standard working solutions.
1.2 working conditions of the apparatus
Liquid chromatography conditions:
a chromatographic column: poroshell 120PFP (2.1 x 100mm, 2.7 μm);
sample introduction amount: 1 mu L of the solution;
column temperature: 40 ℃;
mobile phase: water (a) and acetonitrile (B);
flow rate: 0.2 mL/min;
and (3) an elution mode: gradient elution, wherein the initial proportion A to B is 40 percent to 60 percent; within 0-3 min, gradually changing A: B to 10% and 90% and keeping for 1 min; within 4-4.5 min, the A: B gradually recovers to 40% and 60%, and the time is kept for 2 min.
Mass spectrum conditions:
an ion source: AJS-ESI, nozzle pressure: 45psi, sheath gas temperature: 330 ℃, sheath gas flow rate: 11L/min, atomizing gas flow rate: 5L/min, atomizer temperature: 330 ℃, capillary voltage: 3500V; MRM parameters: and (3) quantifying ions: parent ion 453, daughter ion 369.2, collision energy 20, qualitative ion: parent ion 453, child ion 327.2, collision energy 30.
1.3 sample preparation
A plastic sample is taken, cut into pieces/ground, and the size is not more than 2mm multiplied by 2 mm. 1g of a sample (accurate to 0.1mg) was accurately weighed into a sample bottle, and 10mL of toluene was added thereto. After the bottle cap is screwed down, the sample bottle is put into an ultrasonic cleaning instrument and is subjected to ultrasonic treatment (60 +/-5) min at the temperature of 60 ℃. Taking out the sample bottle, cooling, taking 5mL of supernatant, concentrating to near dryness (0.05-0.1 mL) by using a rotary evaporator, diluting 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 the conditions shown above, wherein isopropylated triphenyl phosphate peaks at 3.67min, and the chromatographic peak shape of the compound is sharp and symmetrical, and no impurity peak interference exists around the retention time.
1.4 Linear equation and detection Limit
The standard stock solution is diluted by toluene to be 5 mug/L, 10 mug/L, 20 mug/L, 50 mug/L, 100 mug/L and 200 mug/L series of standard working solutions. And drawing a standard working curve by taking the mass concentration X (mg/L) as an abscissa and taking 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 quantitation limit for isopropylated triphenyl phosphate
As can be seen from the data in the table, in the linear range of 5 mug/L-200 mug/L, the isopropylated triphenyl phosphate shows good linear relation, and the correlation coefficient is 0.9998. On the basis, the detection Limit (LOD) and the quantification Limit (LOQ) of the standard substance are determined by 3-fold and 10-fold signal-to-noise ratios (S/N), and the detection limit and the quantification limit of the method are respectively 0.013 mu g/L and 0.042 mu g/L.
1.5 recovery and precision
The recovery rate test is carried out by a blank matrix labeling test, a sample without isopropylated triphenyl phosphate to be tested is selected as a blank matrix, and 3 different labeling concentration levels (5 mug/L, 50 mug/L and 200 mug/L) are set. Each spiked level was tested in parallel 3 times (n-3) for precision experiments.
Under the 3 kinds of standard adding levels, the standard adding recovery rate of the isopropylated 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 requirements.
Example 2 Effect of the Experimental conditions
2.1 different mobile phases
Compared with the embodiment 1, the mobile phase is modified as follows: water (A) and methanol (B), the rest conditions being unchanged.
The results show that when water (A) and methanol (B) are selected as mobile phases, the peak emergence time of isopropylated triphenyl phosphate is late, and the peak width is wide, as shown in FIG. 2; when water (A) and acetonitrile (B) are selected as mobile phases, the substance to be detected has symmetrical peak shape, narrow peak width and high response, and no impurity peak interference exists near the retention time, so that water-acetonitrile is selected as the mobile phase.
2.2 different chromatography columns
When a ZORBAX Eclipse XDB-C18 column was used, the remaining conditions were unchanged compared to example 1.
The results show that the response is lower and the peak pattern is asymmetric when the column is replaced by ZORBAX Eclipse XDB-C18 column, as shown in FIG. 3; and by using a Poroshell 120PFP chromatographic column, the isopropylated triphenyl phosphate has high response, is not easily interfered by a matrix, and has symmetrical peak types. Therefore, Poroshell 120PFP chromatography column was the final choice for the experiment.
2.3 different elution conditions
Compared with example 1, the elution mode is as follows: within 0-1 min, the proportion of acetonitrile is 50%; gradually increasing from 50% to 80% within 1-2 min, and keeping for 2 min; and gradually reducing the proportion from 80% to 50% within 4-5 min, and keeping for 3 min. Under the elution condition, the chromatographic peak of isopropylated triphenyl phosphate is interfered by the sample matrix, and the retention time is unstable, as shown in FIG. 4.
2.4 different extraction solvents
Four representative electronic and electric product materials are selected: plastics, wire skin, foam cotton and epoxy resin, then toluene, dichloromethane, methanol, acetonitrile and a 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 among the five different extraction solvents, although dichloromethane has the highest extraction efficiency in plastics and thread skins, the dichloromethane has stronger pertinence and has lower extraction efficiency in foam and epoxy resin; methanol and acetonitrile also have stronger selectivity; the toluene and the mixed solution (n-hexane: acetone ═ 1:1) both have good applicability, the extraction efficiency is comprehensive, and the extraction efficiency of only toluene for each sample can reach more than 85%. The extraction efficiency of the four solvents of dichloromethane, methanol, acetonitrile and mixed solution (n-hexane: acetone ═ 1:1) to the substance to be tested is partially/wholly lower than 85%, and the test requirements cannot be met. Therefore, toluene is best detected as an extraction solvent.
2.5 different extraction conditions
In order to study the effect of extraction temperature and extraction time on the test results, single comparison was performed in the experiment, and the results are shown in fig. 6 and fig. 7. The extraction temperature is respectively selected from 40 ℃ and 60 ℃, the extraction time is respectively selected from 30min, 60min and 90min, and the comparison test result shows that when the ultrasonic temperature is 60 ℃, the recovery rate can reach more than 85%. When the ultrasonic time reaches 60min, the maximum extraction efficiency can be basically reached. Considering practical factors, 60 ℃ ultrasonic for 60min is selected as the optimal extraction condition.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A detection method of isopropylated triphenyl phosphate by a liquid phase tandem mass spectrometer is characterized by 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 supernatant; concentrating the obtained supernatant, diluting with methanol to constant volume to obtain concentrated solution, and filtering the concentrated solution to obtain solution to be detected;
(3) and (3) detecting by using a liquid chromatography tandem mass spectrometer.
2. The detection method according to claim 1, wherein in the step (1), the standard solution is prepared by the following steps:
accurately weighing an isopropylated triphenyl phosphate standard substance, dissolving the isopropylated triphenyl phosphate 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 obtain 5. mu.g/L, 10. mu.g/L, 50. mu.g/L, 100. mu.g/L, and 200. mu.g/L series of standard working solutions.
3. The detection method according to claim 1, wherein in the step (2), the sample to be detected has a size of not more than 2mm x 2 mm.
4. The detection method according to claim 1, wherein in the step (2), the extraction solvent is at least one selected from the group consisting of toluene, dichloromethane, methanol, acetonitrile, a mixed solution of n-hexane and acetone, and is preferably toluene.
5. The detection method according to claim 1, wherein in the step (2), the mass-to-volume ratio of the sample to be detected to the extraction solvent is 1: 8-15 (g: mL), preferably 1:10(g: mL).
6. The detection method according to claim 1, wherein in the step (2), the temperature of the ultrasonic extraction is 50-70 ℃ and the time is 55-80 min; preferably, the temperature of the ultrasonic extraction is 60 ℃, and the time is 60 min.
7. The detection method according to claim 1, wherein the step (2) is specifically:
taking a sample with the size of not more than 2mm multiplied by 2mm, accurately weighing 1g of sample, accurately weighing the sample to 0.1mg, placing the sample into a sample bottle, adding 10mL of methylbenzene into the sample bottle, screwing a bottle cap, placing the sample bottle into an ultrasonic cleaning instrument, performing ultrasonic treatment at 60 ℃ for 60min, taking out the sample bottle, cooling, taking 5mL of supernatant, concentrating the supernatant to be nearly dry by using a rotary evaporator, performing volume fixing to 1-2 mL by using methanol, filtering a proper amount of concentrated solution by using a 0.22 mu m filter membrane, and directly determining.
8. The detection method according to claim 1, wherein in the step (3), the conditions of the liquid chromatography are as follows:
a chromatographic column: PFP or C18 chromatography columns;
sample introduction amount: 1.8-1.2 mu L;
column temperature: 35-45 ℃;
mobile phase: water (a) and acetonitrile (B);
flow rate: 0.18-0.22 mL/min;
and (3) an elution mode: carrying out gradient elution on the mixture,
preferably, the conditions of the liquid chromatography are as follows:
a chromatographic column: poroshell 120PFP (2.1 x 100mm, 2.7 μm);
sample introduction amount: 1 mu L of the solution;
column temperature: 40 ℃;
mobile phase: water (a) and acetonitrile (B);
flow rate: 0.2mL/min of the reaction solution,
and (3) an elution mode: gradient elution, wherein the initial proportion A to B is 40 percent to 60 percent; within 0-3 min, gradually changing A: B to 10% and 90% and keeping for 1 min; within 4-4.5 min, the A: B gradually recovers to 40% and 60%, and the time is kept for 2 min.
9. The detection method according to claim 1, wherein in the step (3), the mass spectrometry conditions are: an ion source: AJS-ESI, nozzle pressure: 45psi, sheath gas temperature: 330 ℃, sheath gas flow rate: 11L/min, atomizing gas flow rate: 5L/min, atomizer temperature: 330 ℃, capillary voltage: 3500V; MRM parameters: and (3) quantifying ions: parent ion 453, daughter ion 369.2, collision energy 20, qualitative ion: parent ion 453, child ion 327.2, collision energy 30.
10. Use of the detection method according to any one of claims 1 to 9 for detecting isopropylated triphenyl phosphate in materials for electronic and electric products, lubricating oils, adhesives, sealants and plastics.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| W. ROSENBERGER等: "Triphenyl phosphate, isopropylated (isopropylated phenyl phosphates, IPPhP) – Determination of isopropylated phenyl phosphates in the workplace air using gas chromatography (GC-MS)", pages 1 - 12 * |
| 张楠 等: "超高效液相色谱-质谱法测定纺织品中禁用的 9 种有机磷阻燃剂", 《分析试验室》, vol. 34, no. 12, pages 1411 - 1414 * |
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