CN108469482B - Method for simultaneously determining phosphorus flame retardant and bromine flame retardant in PVC (polyvinyl chloride) by GC-MS (gas chromatography-Mass spectrometer) - Google Patents
Method for simultaneously determining phosphorus flame retardant and bromine flame retardant in PVC (polyvinyl chloride) by GC-MS (gas chromatography-Mass spectrometer) Download PDFInfo
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Abstract
The invention relates to a method for detecting phosphorus flame retardants and bromine flame retardants in PVC, in particular to a method for simultaneously determining the phosphorus flame retardants and the bromine flame retardants in PVC by GC-MS. The method is simple and convenient to operate, has ideal precision and recovery rate, can realize one-time detection and simultaneous detection of two major types of forbidden flame retardants, and meets the regulatory instruction restriction requirements of the two types of substances.
Description
Technical Field
The invention relates to a method for detecting phosphorus flame retardants and bromine flame retardants in PVC, in particular to a method for simultaneously determining the phosphorus flame retardants and the bromine flame retardants in PVC by using a gas chromatography-mass spectrometry (GC-MS).
Background
In recent years, due to the considerable harm of polybrominated biphenyls and polybrominated diphenyl ether brominated flame retardants to human bodies and the environment, regulations are issued at home and abroad to limit the use of the polybrominated biphenyls and polybrominated diphenyl ether brominated flame retardants, such as 2011/65/EC RoHS instruction of European Union, and a domestic method for limiting the use and management of harmful substances of electric and electronic products. These regulations limit the use of brominated flame retardants and also allow for a significant increase in the market share of other new flame retardants such as organophosphates and the like. However, with the intensive research on the organic phosphate ester compound, the potential carcinogenicity, reproductive toxicity, neurotoxicity and other harmfulness are gradually known, and the risks of the organic phosphate ester compound are increasingly emphasized and regulated in some countries.
At present, although detection methods aiming at brominated flame retardants and organophosphorus flame retardants respectively exist at home and abroad, no method for simultaneously detecting two types of flame retardants exists.
Disclosure of Invention
The invention provides a GC-MS method for simultaneously detecting 8 Organic Phosphate Esters (OPEs), 1-10 polybrominated biphenyls (PBBs) and 1-10 polybrominated diphenyl ethers (PBDEs) in PVC.
The invention is implemented by adopting the following technical means:
a GC-MS method for simultaneously determining phosphorus flame retardants and bromine flame retardants in PVC is characterized by comprising the following steps:
(1) preparing a standard working solution: preparing a mixed solvent from toluene and acetone according to a volume ratio of 2:1, accurately transferring a proper amount of 8 OPEs standard substances, 1-10 polybrominated biphenyls and 1-10 polybrominated diphenyl ethers respectively, adding the mixed solvent to a brown volumetric flask for dissolving, transferring the mixed solvent to a scale mark, obtaining a stock solution with a concentration of 10 mu g/mL, and gradually diluting the stock solution with the mixed solvent to a standard working solution with a concentration of 0.25-5.0mg/L when the stock solution is used;
(2) pretreatment: crushing a sample into small pieces, adding 0.1 +/-0.0001 g of sample into a microwave extraction sleeve, adding 30mL of mixed solvent, mixing, and placing into a microwave extractor for microwave extraction;
(3) microwave extraction: placing the mixed sample in a microwave extraction instrument, heating to 110-120 ℃, keeping for 12-15 min, transferring the extraction liquid to a 50mL volumetric flask after extraction is finished, washing sample residues and a sleeve pipe by using a mixed solvent, collecting all washing liquid in the volumetric flask, and performing constant volume;
(4) GC-MS analysis: filtering an appropriate amount of extract liquid with constant volume to obtain a sample solution for GC-MS analysis;
(5) and obtaining a linear regression equation and a standard curve of the organic phosphate flame retardant by using the detection data of the standard working solution, and obtaining the contents of the phosphorus flame retardant and the brominated flame retardant in the sample by using the detection data of the sample solution through the linear regression equation or the standard curve.
Further, in the step (3), the microwave extraction instrument is arranged to raise the temperature of the mixed sample to 110-120 ℃ within 10 min, and the temperature is maintained for 12-15 min.
Further, in the step (3), for the sample whose content of the substance to be detected is lower than the lowest value of the standard curve, the extract liquid after the extraction is concentrated, preferably, the concentration treatment mode is any one of rotary evaporation or nitrogen purging.
Further, in the step (4), a filter membrane of 0.2-0.45 μm is adopted for filtration.
Further, in the step of GC-MS analysis, chromatographic conditions and mass spectrum conditions are as follows:
chromatographic conditions are as follows: DB-5HT chromatography column (15 m 0.25 mm 0.10 μm); the sample inlet temperature is 300 ℃, the sample injection amount is 1 mu L, and the split-flow sample injection is not carried out; the initial column temperature is 110 ℃, the temperature is kept for 2min, the temperature is increased to 200 ℃ at the speed of 40 ℃/min, then the temperature is increased to 260 ℃ at the speed of 10 ℃/min, and finally the temperature is increased to 340 ℃ at the speed of 20 ℃/min and the temperature is kept for 2 min; the carrier gas is helium, and the flow rate is 1 mL/min;
mass spectrum conditions: an EI ion source, wherein the temperature of the ion source is 250 ℃, and the ionization energy is 70 Ev; the temperature of the transmission line is 300 ℃; the solvent delay was 2.5 min.
The invention has the advantages that:
the work adopts microwave extraction as a pretreatment means to extract two types of flame retardants in PVC, and a gas chromatography-mass spectrometer is used for detection, so that the detection of phosphorus flame retardants and bromine flame retardants in PVC can be realized at one time. The method is simple and convenient to operate, has ideal precision and recovery rate, can realize one-time detection and simultaneous detection of two major types of forbidden flame retardants, and meets the regulatory instruction restriction requirements of the two types of substances.
Drawings
FIG. 1 is a SIM chromatogram of a mixed standard solution of organophosphate, polybrominated biphenyls, and polybrominated diphenyl ethers according to the present invention.
Wherein, the reference numbers of the peak-appearing graph respectively correspond to the following substances:
1.TEPA, 2.1PBB, 3.TBP, 4.1PBDE, 5.TCEP, 6.TCPP, 7.2PBB, 8.2PBDE, 9.3PBB, 10.3PBDE, 11.4PBB, 12.TDCP, 13.TPhP, 14.TBEP, 15.5PBB, 16.4PBDE, 17.TOCP, 18.6PBB, 19.5PBDE, 20.6PBDE, 21.7PBB, 22.7PBDE, 23.8PBB, 24.8PBDE, 25.9PBB, 26.9PBDE, 27.10PBB, 28.10PBDE
Detailed Description
The present invention will be described with reference to specific examples.
The instrument comprises the following steps: 7890B-5977A GC (Agilent technologies, Inc., USA); MARS microwave extractor (pegan, usa);
reagent: tris (3-chloropropyl) phosphate (TCPP), tris (1, 3-dichloro-2-propyl) phosphate (TDCP), tris (2-chloroethyl) phosphate (TCEP), tris (o-tolyl) phosphate (TOCP), triphenyl phosphate (TPhP), tributyl phosphate (TBP), tris (2-butoxyethyl) phosphate (TBEP), tris- (1-aziridinyl) phosphine oxide (TEPA) standard: the purity is more than 95 percent, and is a product of German Dr. Ehrenstontorfer company;
1-10 polybromodiphenyl ether (1-10 PBDE), 1-6,10 bromobiphenyl (1-6, 10 PBB), 7 bromobiphenyl (7PBB), 8 bromobiphenyl (8PBB), 9 bromobiphenyl (9PBB) standard solutions: AccuStandard, Inc., USA;
toluene, acetone: the product of Honeywell company of the United states.
A sample to be tested: taking a plastic sample with a commercially available PVC toy, primarily crushing the plastic sample by a plastic crusher, and continuously finely crushing the plastic sample into small samples with side length less than 5 mm.
Negative samples: taking a PVC plastic sample which does not contain the above two substances to be detected after being detected by the conventional phosphorus flame retardant and bromine flame retardant, and continuously finely crushing the PVC plastic sample into small samples with the side length less than 5mm after the PVC plastic sample is preliminarily crushed by a plastic crusher.
Examples
Preparing a standard working solution: preparing a mixed solvent from toluene and acetone according to a volume ratio of 2:1, accurately transferring a proper amount of 8 OPEs standard substances, 1-10 polybrominated biphenyls and 1-10 polybrominated diphenyl ethers respectively, adding the mixed solvent to a brown volumetric flask for dissolving, transferring the mixed solvent to a scale mark, obtaining a stock solution with a concentration of 10 mu g/mL, and gradually diluting the stock solution with the mixed solvent to standard working solutions with concentrations of 0.25, 0.5, 1.0, 2.5 and 5.0mg/L when the stock solution is used.
Treating a sample to be detected: crushing the PVC sample to be detected into small pieces with the side length less than 5mm, uniformly mixing, weighing 0.1g, accurately weighing 0.0001g, placing the small pieces in a microwave extraction sleeve, adding 30mL of mixed solvent, and placing the small pieces in a microwave extraction instrument. And (3) setting a microwave extraction instrument for 10 min, heating the mixed sample to 110 ℃, keeping the temperature for 15 min after the mixed sample is heated to 110 ℃, transferring the extract liquor to a 50mL volumetric flask after the extraction is finished, washing sample residues and a sleeve pipe by using a small amount of mixed solvent, collecting all washing liquor in the volumetric flask, fixing the volume to a scale mark, taking a proper amount of extract liquor, filtering the extract liquor by a 0.45 mu m filter membrane, and obtaining a sample solution to be detected for GC-MS analysis.
And (3) negative sample treatment: and crushing the PVC sample into small negative PVC samples with the side length less than 5mm, and performing the same treatment process as the treatment of the sample to be detected.
Chromatographic conditions are as follows: DB-5HT chromatography column (15 m 0.25 mm 0.10 μm); the sample inlet temperature is 300 ℃, the sample injection amount is 1 mu L, and the split-flow sample injection is not carried out; the initial column temperature is 110 ℃, the temperature is kept for 2min, the temperature is increased to 200 ℃ at the speed of 40 ℃/min, then the temperature is increased to 260 ℃ at the speed of 10 ℃/min, and finally the temperature is increased to 340 ℃ at the speed of 20 ℃/min and the temperature is kept for 2 min; the carrier gas is helium, and the flow rate is 1 mL/min.
Mass spectrum conditions: an EI ion source, wherein the temperature of the ion source is 250 ℃, and the ionization energy is 70 Ev; the temperature of the transmission line is 300 ℃; solvent delay 2.5 min, scan mode: and selecting ion monitoring SIM mode detection.
And respectively obtaining a linear regression equation and a standard curve of the phosphorus flame retardant and the bromine flame retardant according to the detection data of the standard working solution, and obtaining the content of the phosphorus flame retardant and the bromine flame retardant in the sample according to the detection data of the sample solution through the linear regression equation or the standard curve.
Optimized selection of extraction conditions
Taking the extraction temperature, extraction time, mixed solvent proportion and solvent volume which influence microwave extraction as main influencing factors of an orthogonal experimental method, wherein each factor takes 3 levels, and designing L9(34) And (3) orthogonal design table, wherein orthogonal test is respectively carried out on the positive samples containing TDCP and decabromobiphenyl. And (3) completing 9 groups of tests in each orthogonal test series, carrying out parallel tests on each group for 3 times, taking the average value of the test results as test results, and determining the optimal test conditions according to the results of the positive samples under different extraction conditions, wherein the TDCP results are shown in tables 1 and 2. As can be seen from the calculation results in Table 2, the extraction temperature is the most important factor influencing the extraction effect of the OPEs in the sample, and secondly, the dosage and the extraction time of the extraction solvent, and the proportion of the mixed solvent has no obvious influence on the extraction effect, so the optimization scheme given in Table 2 is A2B3C2D3. The 10PBB results are shown in Table 3, the temperature is also the most influential factor on the extraction effect, and then the solvent ratio, extraction time and solvent amount are mixed separately, and the optimum scheme is A2B3C3D3. According to the above two orthogonal test results, the optimum conditions for the extraction temperature, extraction time and extraction solvent volume are the same for TDCP and 10 PBB; for the extraction solvent ratio, 10PBB is greatly influenced by the solvent and TDCP is not obviously influenced, so the volume ratio of toluene to acetone is selected to be 2: 1. In conclusion, the extraction scheme A is finally determined2B3C3D3Namely, a mixed solvent is prepared by toluene and acetone according to the volume ratio of 2: 1. Therefore, in this example, 30mL of a mixed solution of toluene and acetone in a volume ratio of 2:1 was used as the extraction solvent, and the microwave extraction was performed at an extraction temperature of 110 ℃ for 15 min.
Optimized selection of mass spectrometry conditions
Respectively carrying out mass spectrum full scanning and selective ion scanning analysis on the mixed standard solution of OPEs, polybrominated biphenyls and polybrominated diphenyl ethers, determining the retention time of each target analyte according to the obtained chromatogram in a full scanning mode, selecting fragment ions with less interference and higher abundance as target monitoring ions according to the obtained mass spectrogram, taking the fragment ions with highest abundance as quantitative ions, and carrying out quantitative analysis in a selective ion mode, wherein the specific conditions are shown in tables 4 and 5. Fig. 1 is a SIM chromatogram obtained under established conditions for a mixed standard solution, and it can be seen that, except for the combined peaks of TCPP due to the presence of isomers, the other spectral peaks are completely separated, sharp and symmetrical in shape.
Establishment of a Linear relationship and calculation of detection limits
According to the conditions determined by the method, the standard solutions of the standard working solutions with the concentrations of 0.25, 0.5, 1.0, 2.5 and 5.0mg/L are respectively taken for determination, a standard curve is established according to the corresponding concentrations of the response values, namely, the chromatographic peak area of the SIM chromatogram is selected as the ordinate, the corresponding concentrations are selected as the abscissa, the standard curve is drawn, and the linear relation of the standard curve is determined. The detection Limit (LOD) of the mixed standard solution was calculated under the condition of signal-to-noise ratio (S/N) =3, and the lower limit of quantification (LOQ) was calculated under the condition of signal-to-noise ratio (S/N) = 10. The linear regression equations, correlation coefficients, LOD, LOQ of OPEs, polybrominated biphenyls, and polybrominated diphenyl ethers are shown in tables 6 and 7.
Determination of recovery and precision
Taking a negative PVC sample, respectively adding three OPEs, polybrominated biphenyls and polybrominated diphenyl ether standard solutions with known concentrations, carrying out parallel determination for 7 times according to the experimental conditions and each concentration, and calculating the average recovery rate and the Relative Standard Deviation (RSD), wherein the results are shown in tables 8 and 9, and the average recovery rate and the RSD have no significant difference.
In conclusion, a microwave extraction/gas chromatography-mass spectrometry analysis method for simultaneously measuring 8 organic phosphate compounds such as TCEP and the like, 1-10 polybrominated biphenyls and 1-10 polybrominated diphenyl ethers in PVC is established by taking a mixed solvent of toluene and acetone in a volume ratio of 2:1 as an extraction solvent. The method is simple and convenient to operate, has ideal precision and recovery rate, can realize one-time detection and simultaneous detection of two major types of forbidden flame retardants, and meets the regulatory instruction restriction requirements of the two types of substances.
Test results of samples to be tested
As shown in tables 10 and 11, the following commercially available 8 PVC plastic products were pretreated by the sample treatment method in the examples, and each sample solution was analyzed by GC-MS under the mass spectrum and chromatography conditions in the examples, and the analysis results were as follows:
the results of the measurement of the organic phosphate, polybrominated biphenyls and polybrominated diphenyl ethers of the above-mentioned 8 commercially available PVC plastic products by the present method show that TCEP and 10PBB of only one wire sheath were detected in all the samples, and the contents were 0.265. mu.g/g and 0.268. mu.g/g, respectively.
Claims (5)
1. A GC-MS method for simultaneously determining phosphorus flame retardants and bromine flame retardants in PVC is characterized by comprising the following steps:
step (1): preparing a mixed solvent from toluene and acetone according to a volume ratio of 2:1, accurately transferring a proper amount of 8 OPEs standard substances, 1-10 polybrominated biphenyls and 1-10 polybrominated diphenyl ethers respectively, adding the mixed solvent to a brown volumetric flask for dissolving, transferring the mixed solvent to a scale mark, obtaining a stock solution with a concentration of 10 mu g/mL, and diluting the stock solution into a standard working solution with a concentration range of 0.25-5.0mg/L step by using the mixed solvent when in use;
step (2): crushing a sample into small pieces, adding 0.1 +/-0.0001 g of sample into a microwave extraction sleeve, adding 30mL of the mixed solvent, mixing, and placing into a microwave extractor for microwave extraction;
and (3): placing the mixed sample in a microwave extraction instrument, heating to 110-120 ℃, keeping for 12-15 min, transferring the extraction liquid to a 50mL volumetric flask after extraction is finished, washing sample residues and a sleeve pipe by using the mixed solvent, collecting all washing liquid in the volumetric flask, and performing constant volume;
and (4): filtering an appropriate amount of extract liquid with constant volume to obtain a sample solution for GC-MS analysis;
and (5): obtaining a linear regression equation and a standard curve of the organic phosphate flame retardant by using the detection data of the standard working solution, and obtaining the contents of the phosphorus flame retardant and the brominated flame retardant in the sample by using the detection data of the sample solution through the linear regression equation or the standard curve;
the 8 OPEs standard substances are tris (3-chloropropyl) phosphate, tris (1, 3-dichloro-2-propyl) phosphate, tris (2-chloroethyl) phosphate, tris (o-tolyl) phosphate, triphenyl phosphate, tributyl phosphate, tris (2-butoxyethyl) phosphate and tris- (1-aziridinyl) phosphine oxide standard substances;
in the step (4), the GC-MS analysis is carried out by the following chromatographic conditions and mass spectrum conditions:
chromatographic conditions are as follows: DB-5HT chromatographic column of 15 m × 0.25 mm × 0.10 μm is adopted, the sample inlet temperature is 300 ℃, the sample injection amount is 1 μ L, and split-flow sample injection is not carried out; the initial column temperature is 110 ℃, the temperature is kept for 2min, the temperature is increased to 200 ℃ at the speed of 40 ℃/min, then the temperature is increased to 260 ℃ at the speed of 10 ℃/min, and finally the temperature is increased to 340 ℃ at the speed of 20 ℃/min and the temperature is kept for 2 min; the carrier gas is helium, and the flow rate is 1 mL/min;
mass spectrum conditions: an EI ion source, wherein the temperature of the ion source is 250 ℃, and the ionization energy is 70 Ev; the temperature of the transmission line is 300 ℃; the solvent delay was 2.5 min.
2. The method for simultaneously determining the phosphorus-based and bromine-based flame retardants in PVC according to claim 1, wherein in the step (3), the microwave extractor is arranged to raise the temperature of the mixed sample to 110-120 ℃ within 10 min and maintain the temperature for 12-15 min.
3. The method for simultaneously measuring phosphorus-based and bromine-based flame retardants in PVC by GC-MS as claimed in claim 1, wherein in the step (3), the extract after extraction is concentrated.
4. The method for simultaneously measuring phosphorus-based and bromine-based flame retardants in PVC by GC-MS as claimed in claim 3, wherein the concentration treatment is any one of rotary evaporation or nitrogen purge.
5. The method for simultaneously determining the phosphorus flame retardant and the bromine flame retardant in the PVC by GC-MS as claimed in claim 1, wherein in the step (4), the filtration is performed by using a filter membrane with the diameter of 0.2-0.45 μm.
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| CN109061025B (en) * | 2018-10-26 | 2021-08-10 | 苏州科技大学 | Method for detecting brominated flame retardant content in food |
| CN111650305A (en) * | 2020-07-06 | 2020-09-11 | 中国计量科学研究院 | Method for measuring polybrominated diphenyl ethers and organic phosphates in plastics by gas chromatography-inductively coupled plasma mass spectrometry |
| CN113009011A (en) * | 2021-02-19 | 2021-06-22 | 广东省计量科学研究院（华南国家计量测试中心） | 4,4' -dibromodiphenyl ether purity standard substance and preparation method thereof |
| CN112940030B (en) * | 2021-02-25 | 2023-09-05 | 上海第二工业大学 | Method for extracting environment-friendly halogen-free flame retardant in polarizing film by microwave assistance |
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