CN115015421B - Method for rapidly determining additive in food contact material - Google Patents
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- CN115015421B CN115015421B CN202210620118.9A CN202210620118A CN115015421B CN 115015421 B CN115015421 B CN 115015421B CN 202210620118 A CN202210620118 A CN 202210620118A CN 115015421 B CN115015421 B CN 115015421B
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 30
- 239000000654 additive Substances 0.000 title claims abstract description 24
- 230000000996 additive effect Effects 0.000 title claims description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 17
- 238000003795 desorption Methods 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 7
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- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 claims description 5
- 238000004817 gas chromatography Methods 0.000 claims description 5
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000011550 stock solution Substances 0.000 claims description 5
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 claims description 4
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003517 fume Substances 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- -1 UV-312 Chemical compound 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001819 mass spectrum Methods 0.000 claims description 3
- 238000004451 qualitative analysis Methods 0.000 claims description 3
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- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 2
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- 238000001514 detection method Methods 0.000 abstract description 18
- 238000005516 engineering process Methods 0.000 abstract description 2
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- 238000002076 thermal analysis method Methods 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 13
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- 239000004033 plastic Substances 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000011835 investigation Methods 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
- 238000002372 labelling Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- 238000012106 screening analysis Methods 0.000 description 2
- 238000012764 semi-quantitative analysis Methods 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 238000002098 selective ion monitoring Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for rapidly determining additives in food contact materials, which can rapidly analyze and detect 20 additives in the food contact materials by using a tube furnace cracker-gas chromatography-mass spectrometry technology, is simple in operation and provides a new method for food safety detection.
Description
Technical Field
The invention relates to the field of food detection and analysis, in particular to a thermal analysis-gas chromatography-mass spectrometry combined method for rapidly determining 20 additives in food contact plastics.
Background
The plastic food contact plastic is easy to age and degrade in the use process, and antioxidants and ultraviolet absorbers can be added to delay the aging and degradation process in the process of processing and producing the food contact plastic material. Among them, phenolic, phosphite and aminic antioxidants are widely used because they can effectively retard oxidation of plastic food-contact materials, and benzotriazole and benzophenone ultraviolet absorbers are widely used because they can effectively retard photodegradation of plastic food-contact materials. These additives can migrate into the food during use of the food contact material and cause harm to the human body. The national standard GB 9685-2016 records various antioxidants and ultraviolet absorbers, and provides the application range, the maximum application amount and the specific migration amount.
The detection methods of antioxidants and ultraviolet absorbers in food contact materials at present mainly comprise liquid chromatography, gas chromatography, liquid chromatography tandem mass spectrometry, gas chromatography-mass spectrometry and the like, and mainly focus on measuring migration amounts of antioxidants and ultraviolet absorbers in food simulants such as water, acid, alcohol and oil. These methods are complicated in pretreatment process, long in detection period, and require the use of a large amount of organic solvent. Meanwhile, in the detection method reported in the prior art, the detection rate of the antioxidant and the ultraviolet absorbent is low, the antioxidant and the ultraviolet absorbent are mainly detected in high-concentration alcohol simulants and oil simulants, and the migration quantity of the antioxidant and the ultraviolet absorbent does not exceed the requirement of the migration limit specified in GB 9685-2016. It is therefore desirable to establish an analytical method for rapid screening of antioxidants and ultraviolet absorbers in food contact materials.
The technical scheme of the invention adopts a thermal analysis-gas chromatography-mass spectrometry technology, does not need a complex pretreatment process, has the advantages of small sample consumption, direct sample injection analysis of solid samples, short detection period and the like, and can be widely used for rapid screening of toxic and harmful substances in food contact materials.
Disclosure of Invention
The invention aims to provide a method for rapidly determining an additive in a food contact material, which shortens the detection period and provides a reliable detection means for food safety.
The aim of the invention is achieved by the following technical scheme:
A method for rapidly determining 20 additives in a food contact material, comprising performing qualitative analysis and/or external standard quantitative analysis on the food contact material by adopting a thermal analysis-gas chromatography-mass spectrometry method; wherein the 20 additives are BHA, 2, 4-di-tert-butylphenol, BHT, antioxidant BHEB, antioxidant D, antioxidant 2246, antioxidant 308, antioxidant 425, antioxidant 168, antioxidant 1076, benzophenone, UV-9, UV-P, UV-24, UV-326, UV-329, UV-312, UV-328, UV-327 and UV-531.
In particular, the method for rapidly determining 20 additives in food contact materials comprises the following steps:
(1) A sample of the food contact material was cut into pieces no greater than 0.5mm by 0.5mm as a sample, and an accurately weighed amount of the sample was added to a pyrolysis cuvette.
(2) And analyzing the sample added into the pyrolysis cuvette by adopting a thermal analysis-gas chromatography-mass spectrometry combined instrument, determining the peak outlet time and the peak area of 20 additives, and calculating according to a standard working curve to obtain the content of 20 additives in the sample.
Further, the method for rapidly determining 20 additives in the food contact material further comprises the following steps of:
(1) 50mg of each of the 20 additives was weighed, dissolved in methylene chloride, and transferred to a 50mL brown volumetric flask to determine the volume, to prepare 1000mg/L of a mixed standard stock solution.
(2) The stock solution was diluted stepwise with methylene chloride to obtain a series of 10mg/L, 20mg/L, 50mg/L, 100mg/L, 200mg/L standard working solutions.
(3) And accurately measuring 5 mu L of the series of standard working solutions, injecting the series of standard working solutions into a pyrolysis cuvette, placing the cuvette in a fume hood for 20min, and after the solutions volatilize, analyzing by adopting a thermal analysis-gas chromatography-mass spectrometry combined instrument, and preparing a standard working curve by taking the mass concentration of the compounds in 20 as an abscissa and the peak area as an ordinate.
The conditions of the tube furnace cracker were: the cracking temperature is 300 ℃, the interface temperature is 310 ℃, and the thermal analysis time is 0.3min.
The conditions of the gas chromatography were: HP-5MS (30 m. Times.0.25 mm. Times.0.25 μm) column, temperature program: maintaining at 100deg.C for 1min, heating to 315 deg.C at 20deg.C/min, and maintaining for 6min. The post-operation temperature is 315 ℃, and the post-operation time is 5min; the temperature of the sample inlet is 300 ℃, the split sample injection is carried out, and the split ratio is 50:1; the carrier gas is high-purity helium (purity is more than 99.999 percent), and the flow rate is 1.0mL/min; solvent delay: 4min; the transmission line temperature was 320 ℃.
The mass spectrum conditions are as follows: electron bombardment ionization source (EI), ion source temperature 230 ℃, quaternary rod temperature 150 ℃. The ionization energy was 70eV. And (3) qualitative in a full scanning mode, wherein the mass number range is 35-600 amu, and quantitative in an ion monitoring mode is selected.
The results showed that the mixed standard solution was analyzed under the above conditions, and the peaks were completely separated from each other.
In this example, the qualitative analysis was performed using full scan, and the quantitative analysis was performed using the selected ion monitoring mode. The fragment ions with relatively high abundance, large mass number and small interference are selected from the fragment ions of each compound according to the mass spectrogram to serve as characteristic target monitoring ions for measurement and confirmation, and characteristic ions and quantitative ions of each target compound are shown in table 1.
TABLE 1 retention time of 20 additives and characteristic ions
Both the standard solution and the sample to be measured were measured under the above conditions, and if the sample to be measured and the standard reference sample have peaks at the same retention time, they were confirmed using table 1.
Through confirmation analysis, if the retention time of the spectrum peak of the measured object in the sample to be measured is consistent with that of the standard substance, and in the spectrum of the sample after background subtraction, the reference qualitative ions in table 1 are all present, and the abundance ratio of each qualitative ion is consistent with that of the standard substance within the allowable deviation range, the component can be considered to be detected.
The scheme has the following beneficial effects:
The method and the device can finally successfully and rapidly separate and detect 20 additives in the food plastic contact material by selecting proper thermal analysis temperature, time, interface temperature and gas chromatography conditions, proper temperature rise program and proper characteristic target ions.
In addition, the invention has the following advantages:
1. By using the tube furnace cracker, the solid sample can be directly injected without complex pretreatment with chemical solvents, and the detection period is shortened.
2. Establishes a rapid screening and semi-quantitative analysis method of 20 additives in the plastic food contact material, and provides a powerful guarantee for guaranteeing the food safety.
3. The method is simple to operate, high in analysis speed, good in recovery rate and precision, low in detection limit and capable of meeting the daily detection requirements of 20 additives in plastic food contact materials.
Drawings
FIG. 1 shows a GC/MS-SIM diagram of example 1 test samples.
Detailed description of the preferred embodiments
The present invention will be further described with reference to specific examples, which are not intended to limit the scope of the invention, for the purpose of facilitating understanding by those skilled in the art.
Example 1
1. Preparation of standard solutions
Accurately weighing 50mg of each target analyte in a brown volumetric flask, dissolving the target analytes in dichloromethane, and then fixing the volume to 50mL to obtain 1000mg/L mixed standard stock solution.
2. Preparation of positive samples
2.5G of Polycarbonate (PC) pellets containing no target was weighed out accurately, and a polymer solution having a concentration of 25mg/ml was prepared by dissolving the pellets with methylene chloride by ultrasonic. mu.L of polymer solution and 5. Mu.L of standard solution were injected into the sample cup using a microinjector. The sample cup was placed in a fume hood until the solvent was completely evaporated, and a positive test sample was obtained.
3. Detection analysis
Weighing 0.5mg of the standard sample in the step 2, placing the standard sample in a pyrolysis cup, and directly measuring the standard sample by using a thermal analysis-gas chromatography-mass spectrometer.
4. Instrument conditions
Tube furnace cracker:
thermal analysis temperature: 300 ℃; thermal analysis time: 0.3min, interface temperature: 310 ℃.
Gas chromatography:
HP-5MS (30 m. Times.0.25 mm. Times.0.25 μm) column, temperature program: maintaining at 100deg.C for 1min, heating to 315 deg.C at 20deg.C/min, and maintaining for 6min. The post-operation temperature is 315 ℃, and the post-operation time is 5min; the temperature of the sample inlet is 300 ℃, the split sample injection is carried out, and the split ratio is 50:1; the carrier gas is high-purity helium (purity is more than 99.999 percent), and the flow rate is 1.0mL/min; solvent delay: 4min; the transmission line temperature was 320 ℃.
The conditions for mass spectrometry were as follows:
The mass spectrum conditions are as follows: electron bombardment ionization source (EI), ion source temperature 230 ℃, level four, rod temperature 150 ℃, ionization energy 70eV. The quality is characterized by a full scanning mode, and the mass number range is 35-600 amu. Ion monitoring mode quantification is selected.
The results showed that the mixed standard solution was analyzed under the above conditions, and the peaks were completely separated from each other, and the results are shown in FIG. 1.
Example 2: thermal analysis temperature investigation
Setting the thermal desorption time to be 0.2min, setting the interface temperature to be 310 ℃, starting the thermal desorption temperature from 270 ℃, heating the temperature to be 10-330 ℃ each time, and examining the change condition of the peak area and the total peak area of each target compound at different thermal desorption temperatures.
The rest of the procedure is the same as in example 1. The examination results are shown in Table 2.
TABLE 2 influence of thermal analysis temperature
Analysis of results: as a result, it was found that, when the thermal desorption temperature was raised from 270 ℃ to 300 ℃, the peak area of each compound as a whole showed a tendency to gradually increase as the thermal desorption temperature was raised. When the thermal desorption temperature reaches 300 ℃, the thermal desorption temperature is continuously increased, and the peak area of the compound shows two change trends: firstly, the peak areas gradually decrease, such as UV-P, UV-329, antioxidant 425, antioxidant 1076 and the like, and secondly, the peak areas do not change greatly, such as BHA, BHT, UV-328 and the like. Meanwhile, the influence of the thermal desorption temperature on the total peak areas of 20 target compounds is examined, and the result shows that when the thermal desorption temperature is 300 ℃, the total peak areas of 20 target compounds are the largest, so that the thermal desorption temperature is selected to be 300 ℃.
Example 3: investigation of thermal analysis time
The thermal analysis temperature was set at 300℃and the interface temperature was set at 310℃to examine the variation of the peak area and the total peak area of each target compound at different thermal analysis times (0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 min).
The rest of the procedure is the same as in example 1. The examination results are shown in Table 3.
TABLE 3 influence of thermal analysis time
The results showed that the peak area of most compounds increased with increasing thermal desorption time before 0.3min, and the peak area showed a gradually decreasing trend when thermal desorption time increased from 0.3min to 0.7min, such as antioxidant 168, antioxidant 425, 2, 4-di-t-butylphenol, etc., all showed the above-mentioned trend. However, some compounds reach the maximum peak area at 0.2min, and the thermal desorption time is continuously increased, so that the peak area is not changed greatly, such as UV-P, UV-312. The effect of the thermal analysis time on the total peak area of 20 target compounds was also examined, and the result showed that the total peak area of 20 target compounds was maximum when the thermal analysis time was 0.3min, so the thermal analysis time was selected to be 0.3min.
Example 4: investigation of interface temperature
Setting the thermal analysis temperature to 300 ℃, the thermal analysis time to 0.3min, and the interface temperature to 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃ and 330 ℃ respectively, and examining the variation condition of the peak area and the total peak area of each target compound at different interface temperatures.
The rest of the procedure is the same as in example 1. The examination results are shown in Table 4.
TABLE 4 influence of interface temperature
The results show that the interface temperature has little influence on partial compounds such as BPN, UV-24, UV-326 and the like, and the whole appearance is that the peak area slightly increases along with the increase of the interface temperature; the influence on partial compounds such as antioxidant 308, antioxidant 425, UV-328 and the like is larger, the peak area gradually increases along with the increase of the interface temperature, the peak area reaches the maximum value when the interface temperature increases to 310 ℃, the interface temperature is continuously increased, the peak area change is not large, meanwhile, the total peak area of 20 compounds is taken as a judgment basis, and the total peak area is the maximum when the interface temperature is 310 ℃, so that the interface temperature is selected to be 310 ℃.
Example 5: investigation of GC-MS conditional split ratio
The split ratio of the sample inlet is respectively set to be 20: 1. 50:1 and 100:1, 5 mu L of standard solution is directly added into a sample cup, and the sample is injected and analyzed after being placed in a fume hood for 20min. The rest of the procedure is the same as in example 1.
The results show that when the split ratio is 20:1, the pressure change of the sample inlet after sample injection is larger, and the retention time fluctuation of each compound is larger. When the split ratio is 50:1, the pressure change of the sample inlet is smaller, and the contrast split ratio is 100:1, each compound had a higher response value, so the split ratio was chosen to be 50:1.
Example 6: investigation of GC-MS conditional temperature elevation procedure
The temperature of column Wen Chushi was set at 100deg.C and the effect of four ascending rate sequences of 10, 15, 20 and 25 deg.C/min on the analysis time and degree of separation of each compound was examined. The rest of the procedure is the same as in example 1.
The results show that each compound was able to achieve better separation with minimal total analysis time when warmed up at 20 ℃/min programming.
Example 7: investigation of the Linear Range and detection Limit of the GC-MS Condition method
Standard solutions of a series of concentrations were analyzed according to the GC-MS conditions of example 1, and a working curve was drawn with the peak area of each compound on the ordinate and the corresponding mass concentration on the abscissa, with the remainder of the procedure being as in example 1. Table 5 shows the linear range, linear equation and correlation coefficient (r) for 20 compounds.
TABLE 5 Linear equation, linear Range and correlation coefficient for 20 Compounds
The results show that 20 target compounds show good linear relationship in the range of 10-200 mg/L. And respectively taking blank PC, PET, ABS as a matrix, preparing a test sample of 30mg/kg for measurement, wherein the signal to noise ratio of each compound is more than 3, so that the detection limit of the method is set to be 30mg/kg, and the limit requirement of GB 9685-2016 on each compound is completely met.
Example 8: recovery rate and precision investigation of the method
Three blank samples PC, PET, ABS which do not contain the target object are selected, positive samples of 100mg/kg, 500mg/kg and 1000mg/kg are respectively prepared for standard recovery and precision experiments, each level is measured for 3 times in parallel, and the average standard recovery rate and precision are calculated.
Using PC, PET, ABS blank samples as a matrix, standard test samples of 1000mg/kg were prepared for labeling recovery and precision experiments, each level was measured in parallel 3 times, the labeling recovery and precision were calculated, and the rest of the operations were the same as in example 1, and the results are shown in Table 6.
TABLE 6 recovery and precision of 20 Compounds
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The results show that the average labeling recovery rate of each compound in different materials is slightly different, wherein the recovery rate of antioxidant 1076 in PC, PET, ABS materials is the largest difference: the antioxidant 1076 has better recovery rate in PC and PET materials, and slightly lower recovery rate in ABS materials. The average recovery rate of each compound is 68.6-109.0%, and the RSD value is 1.37-11.84%, which shows that the method has better reproducibility and recovery rate.
Example 10: sample testing
42 Commercially available food contact materials and products were tested as described in example 1.
In order to verify the accuracy of the detection result, the positive samples were measured by a dissolution precipitation method and a soxhlet extraction method, respectively: the method comprises the steps of weighing samples with the material of PC, ABS, PS, respectively weighing 0.1g, respectively dissolving the samples with 3mL of dichloromethane by ultrasonic, adding 7mL of methanol to precipitate a polymer, centrifuging, and taking supernatant for machine measurement; since the PP sample is not easily dissolved at normal temperature, dichloromethane is selected as an extraction solvent, after soxhlet extraction is performed for 8 hours, the extract is concentrated to a constant volume and then measured by a machine, and the detection results are summarized in table 7.
TABLE 7 commercial sample detection results
Results: as can be seen from Table 7, antioxidants 168, 1076, 2, 4-di-tert-butylphenol and UV-329 were detected in the five samples, respectively. The measurement results of the method established in the invention are smaller than those of the other two methods, and the measurement results are 64.1 to 91.0 percent of those of the other two methods, which indicates that the method established in the invention has better accuracy and is suitable for rapid screening and semi-quantitative analysis of 20 additives in plastic food contact materials.
The above embodiments are preferred embodiments of the present invention, and besides, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Claims (5)
1. A method for rapidly determining 20 additives in a food contact material, which is characterized in that a thermal analysis-gas chromatography-mass spectrometry method is adopted to perform qualitative analysis and/or external standard quantitative analysis on the food contact material; wherein the additive is BHA, 2, 4-di-tert-butylphenol, BHT, antioxidant BHEB, antioxidant D, antioxidant 2246, antioxidant 308, antioxidant 425, antioxidant 168, antioxidant 1076, benzophenone, UV-9, UV-P, UV-24, UV-326, UV-329, UV-312, UV-328, UV-327 and UV-531,
The conditions of the tube furnace cracker were: the thermal desorption time is 0.1min-0.7min, the thermal desorption temperature is 270-330 ℃, and the interface temperature is 270-330 ℃;
The conditions for gas chromatography were as follows:
chromatographic column: HP-5MS chromatographic column, 30m x 0.25mm x 0.25 [ mu ] m;
Heating program: the initial temperature is 100 ℃, kept for 1.0min, and is raised to 315 ℃ at the speed of 20 ℃/min, kept for 6.0min, and then the operation temperature is 315 ℃ and the operation time is 5.0min;
Sample inlet temperature: 300 ℃.
2. The method according to claim 1, comprising the steps of:
s1, cutting a food contact material sample into fragments with the diameter of not more than 0.5mm multiplied by 0.5mm to serve as a sample, accurately weighing a certain amount of the sample, and adding the sample into a pyrolysis cuvette;
s2, analyzing the sample added into the pyrolysis cuvette by adopting a thermal analysis-gas chromatography-mass spectrometer, determining the peak outlet time and the peak area of 20 additives, and calculating according to a standard working curve to obtain the content of 20 additives in the sample.
3. The method of claim 1, wherein the conditions of the gas chromatograph further comprise:
Transmission line temperature: 320 ℃;
carrier gas: helium with purity >99.999%;
flow rate: 1.0mL/min;
split ratio: 50:1;
Solvent delay: 4.0min.
4. The method of claim 1, wherein the conditions of the mass spectrum are as follows:
Ion source temperature: 230 ℃;
quadrupole temperature: 150 ℃;
ionization mode: EI;
Ionization energy: 70eV;
using full scan mode characterization, ion monitoring mode quantification was selected.
5. The method of claim 1, further comprising the step of creating a standard operating curve:
s1, respectively weighing 50mg of each of 20 additives, dissolving with dichloromethane, transferring into a 50mL brown volumetric flask for constant volume, and preparing a 1000mg/L mixed standard stock solution;
S2, gradually diluting the stock solution by using dichloromethane to obtain 10mg/L, 20mg/L, 50mg/L, 100mg/L and 200mg/L series standard working solutions;
S3, accurately measuring 5 mu L of the standard working solution, injecting the standard working solution into a pyrolysis cup, placing the standard working solution in a fume hood for 20min, and after the solution volatilizes, analyzing the solution by adopting a thermal analysis-gas chromatography-mass spectrometry combined instrument, and manufacturing a standard working curve by taking the mass concentration of 20 compounds as an abscissa and the peak area as an ordinate.
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