CN103760253A - Rapid detection method for plasticizer - Google Patents
Rapid detection method for plasticizer Download PDFInfo
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- CN103760253A CN103760253A CN201410001568.5A CN201410001568A CN103760253A CN 103760253 A CN103760253 A CN 103760253A CN 201410001568 A CN201410001568 A CN 201410001568A CN 103760253 A CN103760253 A CN 103760253A
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Abstract
The invention discloses a rapid detection method for a plasticizer. The rapid detection method comprises the steps of preparation of a plasticizer mixture standard solution, preparation of a plasticizer mixture standard working solution, sample treatment and sample detection; through adding the dosage of an extracting agent, the pre-treatment time of a sample is shortened by extracting and concentrating, so as to realize the purpose of rapid detection. The sample treatment time according to the method is far less than that of a national standard method, and the rapid detection method disclosed by the invention is suitable for screening mass samples in a basic laboratory. The current situations that the pretreatment of the sample in the test is trouble, both time and labor are wasted, and furthermore, the detection cost is high, are changed.
Description
Technical field
The present invention relates to a kind of detection method of plasticiser, relate in particular to a kind of method of the plasticiser fast detecting that shortens the sample pretreatment time.
Background technology
Plasticiser is also plastifier, can reduce high polymer material glass transition temperature and improve the auxiliary agent of plasticity.Industrial, additive when plasticiser is plasthetics moulding, plasticiser kind is much over one hundred, is the compound that a group is called phthalate, for example: DEHP, DINP, DBP, DIDP, BBP, DNOP, DEP and DMP but use the most general.To the query of this type of plasticiser security, mainly come from its oestrogen-like hormone effect, may cause male endocrine disorder, cause sperm quantity to reduce, degradation under fecundity.Therefore the absorption meeting of plasticiser causes huge injury to health, so the Fast Detection Technique of plasticiser is extremely important for safeguarding human security.
At present, the conventional sample-pretreating method of the detection of " plasticiser " is first to adopt liquid-liquid extraction, then through SPE post and gel permeation chromatograph (GPC), purifies; Instrument analytical method has GC method, HPLC method, GC-MS method.Due to the desired laboratory sample pre-service of existing detection technique trouble, not only time-consuming, effort but also testing cost are high,, can not serve as one detection method quickly and easily.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of extraction concentration method that adopts and shortens the sample preparation time, improves the plasticiser method for quick of detection efficiency.
For solving the problems of the technologies described above, the technical solution used in the present invention is: plasticiser method for quick, the preparation of plasticiser mixed standard solution, sample preparation and sample determination step, its innovative point is: in described sample preparation step, sample is carried out respectively to different processing according to not containing oil sample, pure oil sample and containing oil sample three classes.
Further, described sample detection is specially:
(1) the first removing carbon dioxide of sample needs that contains carbon dioxide gas, adds normal hexane 10mL, ultrasonic extraction 5min, and stratification, gets supernatant and measures;
(2) grease sample is 1:1 by volume ratio ethyl acetate and cyclohexane mixed liquor are settled to 50mL, vortex mixed 5min, and after 0.45 μ m membrane filtration, filtrate concentrated by rotary evaporation, to 2.0mL, is measured;
(3) oil-containing sample first adds 20mL sherwood oil vortex mixed 2min, standing rear extraction petroleum ether layer, use again 10mL petroleum ether layer repeated washing triangular flask, carry out altogether three times, merge petroleum ether layer, be evaporated to dry, the ethyl acetate that is 1:1 by volume ratio and cyclohexane mixed liquor are settled to 50mL, and vortex mixed 5min, after 0.45 μ m membrane filtration, filtrate concentrated by rotary evaporation, to 2.0mL, is measured.
Further, in described step (1) in the situation that layered effect is bad, with the centrifugal 5min of speed of 5000r/min.
Further, described normal hexane, ethyl acetate, cyclohexane are all the residual level of agriculture reagent, and sherwood oil is that boiling range is the sherwood oil of 30 ℃～60 ℃.
Further, the preparation of plasticiser mixed standard solution: the storing solution that is 100mg/L with normal hexane constant volume by hybrid standard product, under 4 ℃ ± 1 ℃ condition, preserve, then with normal hexane, be diluted to standard series point stand-by.
Further, in described sample determination process, use gas chromatograph-mass spectrometer (GCMS), adopt the method for split sampling, described condition determination is:
A) gas phase condition:
Chromatographic column: (30m × 0.25mm × 0.25 μ m) for HP-5MS capillary chromatographic column; Injector temperature: 250 ℃; Split sampling, split ratio 5:1; Carrier gas: helium, purity 99.999%; Column temperature: 60 ℃, keep with 20 ℃/min speed, being warming up to 220 ℃ of maintenance 1min after 1min, then be warming up to 280 ℃ with 5 ℃/min, keep 5min; Flow rate of carrier gas: 1.0mL/min; Sample size: 1 μ L;
B) mass spectrum condition: electron impact ion source; Electron-multiplier voltage 1301ev; Ionization voltage 70ev; 230 ℃ of ion source temperatures; 150 ℃ of quadrupole rod temperature; 280 ℃ of interface temperature; SIM/ full scan (SCAN) drainage pattern, quality of scanning scope: m/z 30～350; Solvent delay time 5min; Sample frequency 2.
Further, described qualitative and quantitative analysis is qualitative according to library searching, adopt standard items comparison to determine sample composition, adopt external standard curve method quantitative, concrete is: sample liquid to be measured and standard items select chromatography of ions peak to occur at identical retention time place, and the mass-to-charge ratio of corresponding ms fragment ion is consistent with standard items, its abundance ratio compared with standard items deviation within ± 25% deviation.Adopt the quantitative measurement of external standard curve method, take concentration of standard solution as horizontal ordinate, quota ion peak area is ordinate separately, makes equation of linear regression, more quantitative with sample peak area and typical curve.
Beneficial effect: what the present invention adopted is that the concentrated mode of extraction is carried out sample pre-treatments, and the amount of passing through to increase extraction agent normal hexane in sample is to shorten extraction time.For containing oils sample, do not need gel chromatography device to purify, the sample preparation time, far less than the national standard method processing time, is adapted at when laboratories does a large amount of sample screening using.Changed sample pretreatment trouble in experiment, not only time-consuming, effort but also the high present situation of testing cost.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is elaborated.
One, reagent
1) normal hexane, ethyl acetate, cyclohexane are all the residual level of agriculture reagent, and it is pure that other agents useful for same such as sherwood oil (30 ℃～60 ℃ of boiling ranges), acetone are analysis.
Experimental water is the ultrapure water of Mi Libo ultrapure water instrument system.
2) 16 kinds of plasticisers are that phthalic ester hybrid standard product are purchased from Town in Shanghai spectrum company
Plasticiser mixed standard solution: the storing solution that is 100mg/L with normal hexane constant volume by hybrid standard product keeps in Dark Place in 4 ℃ of refrigerators.
3) plasticiser hybrid standard is used liquid: standard reserving solution is diluted to normal hexane to concentration is 0.5,1,2,4, the standard series point of 8mg/L is stand-by.
Two, instrument
1) major equipment: Agilent7890-5975 gas chromatograph-mass spectrometer (GCMS) (U.S. Agilent company);
2) utility appliance: BIOFUGE STRATOS high-speed refrigerated centrifuge (U.S. Thermo Fisher company); Vortex mixed instrument JH-2(Nantong Kai Ye Science and Technology Ltd.); Ultrasonic washing instrument TY-2A(Suzhou Ke Li company); Rotary Evaporators (Switzerland's step fine jade); Food masher (JiuYang Co., Ltd).
Embodiment 1
1) sample preparation: accurately take 10.0mL soda sample, first removing carbon dioxide, adds normal hexane 10mL, ultrasonic extraction 5min, stratification (the bad centrifugal 5min of 5000r/min that makes of layered effect), gets supernatant and measures, and does reagent blank simultaneously;
2) sample determination:
A) gas phase condition:
Chromatographic column: (30m × 0.25mm × 0.25 μ m) for HP-5MS capillary chromatographic column
Injector temperature: 250 ℃;
Split sampling, split ratio 5:1;
Carrier gas: helium, purity 99.999%;
Column temperature: 60 ℃, keep with 20 ℃/min speed, being warming up to 220 ℃ of maintenance 1min after 1min, then be warming up to 280 ℃ with 5 ℃/min, keep 5min;
Flow rate of carrier gas: 1.0mL/min;
Sample size: 1 μ L;
B) mass spectrum condition: electron impact ion source; Electron-multiplier voltage 1301ev; Ionization voltage 70ev; 230 ℃ of ion source temperatures; 150 ℃ of quadrupole rod temperature; 280 ℃ of interface temperature; SIM/ full scan (SCAN) drainage pattern, quality of scanning scope: m/z 30～350; Solvent delay time 5min; Sample frequency 2;
3) qualitative and quantitative analysis: sample liquid to be measured and standard items select chromatography of ions peak to occur at identical retention time place (± 0.5%), and the mass-to-charge ratio of corresponding ms fragment ion is consistent with standard items, its abundance ratio compared with standard items deviation within ± 25% deviation.Adopt the quantitative measurement of external standard curve method, take concentration of standard solution as horizontal ordinate, quota ion peak area is ordinate separately, makes equation of linear regression, more quantitative with sample peak area and typical curve.
The present embodiment recovery of standard addition is 90.9%～101.2%.
embodiment 2
Accurately take 10.0109g grease sample, with ethyl acetate: cyclohexane (V/V=1) is settled to 50mL, vortex mixed 5min, after 0.45 μ m membrane filtration, filtrate concentrated by rotary evaporation, to 2.0mL, is measured, assay method is with embodiment 1, and the present embodiment recovery of standard addition is 90.1%～105.1%.
embodiment 3
Accurately take 10.0798g sausage sample, first add 20mL sherwood oil vortex mixed 2min, standing rear extraction petroleum ether layer, use again 10mL petroleum ether layer repeated washing triangular flask, carry out altogether three times, merge petroleum ether layer, be evaporated to dry, with ethyl acetate: cyclohexane (V/V=1) is settled to 50mL, and vortex mixed 5min, after 0.45 μ m membrane filtration, filtrate concentrated by rotary evaporation is to 2.0mL, measure, assay method is with embodiment 1, the present embodiment recovery of standard addition 86.9%～106.2%.
Claims (8)
1. plasticiser method for quick, the preparation of plasticiser mixed standard solution, sample preparation and sample determination step, is characterized in that: in described sample preparation step, sample is carried out respectively to different processing according to not containing oil sample, pure oil sample and containing oil sample three classes.
2. plasticiser method for quick according to claim 1, is characterized in that: described sample detection is specially:
(1) the first removing carbon dioxide of sample needs that contains carbon dioxide gas, adds normal hexane 10mL, ultrasonic extraction 5min, and stratification, gets supernatant and measures;
(2) grease sample is 1:1 by volume ratio ethyl acetate and cyclohexane mixed liquor are settled to 50mL, vortex mixed 5min, and after 0.45 μ m membrane filtration, filtrate concentrated by rotary evaporation, to 2.0mL, is measured;
(3) oil-containing sample first adds 20mL sherwood oil vortex mixed 2min, standing rear extraction petroleum ether layer, use again 10mL petroleum ether layer repeated washing triangular flask, carry out altogether three times, merge petroleum ether layer, be evaporated to dry, the ethyl acetate that is 1:1 by volume ratio and cyclohexane mixed liquor are settled to 50mL, and vortex mixed 5min, after 0.45 μ m membrane filtration, filtrate concentrated by rotary evaporation, to 2.0mL, is measured.
3. plasticiser method for quick according to claim 2, is characterized in that: in described step (1) in the situation that layered effect is bad, with the centrifugal 5min of speed of 5000r/min.
4. plasticiser method for quick according to claim 2, is characterized in that: described normal hexane, ethyl acetate, cyclohexane are all the residual level of agriculture reagent, and sherwood oil is that boiling range is the sherwood oil of 30 ℃～60 ℃.
5. plasticiser method for quick according to claim 1, it is characterized in that: plasticiser mixed standard solution preparation: the storing solution that is 100mg/L by hybrid standard product normal hexane constant volume, under 4 ℃ ± 1 ℃ condition, preserve, then with normal hexane, be diluted to standard series point stand-by.
6. plasticiser method for quick according to claim 1, is characterized in that: in described sample determination process, use gas chromatograph-mass spectrometer (GCMS), adopt the method for split sampling, described condition determination is:
A) gas phase condition:
Chromatographic column: (30m × 0.25mm × 0.25 μ m) for HP-5MS capillary chromatographic column; Injector temperature: 250 ℃; Split sampling, split ratio 5:1; Carrier gas: helium, purity 99.999%; Column temperature: 60 ℃, keep with 20 ℃/min speed, being warming up to 220 ℃ of maintenance 1min after 1min, then be warming up to 280 ℃ with 5 ℃/min, keep 5min; Flow rate of carrier gas: 1.0mL/min; Sample size: 1 μ L;
B) mass spectrum condition: electron impact ion source; Electron-multiplier voltage 1301ev; Ionization voltage 70ev; 230 ℃ of ion source temperatures; 150 ℃ of quadrupole rod temperature; 280 ℃ of interface temperature; SIM/ full scan (SCAN) drainage pattern, quality of scanning scope: m/z 30～350; Solvent delay time 5min; Sample frequency 2.
7. plasticiser method for quick according to claim 1, it is characterized in that: described qualitative and quantitative analysis is qualitative according to library searching, adopt standard items comparison to determine sample composition, adopt external standard curve method quantitative, concrete is: sample liquid to be measured and standard items select chromatography of ions peak to occur at identical retention time place, and the mass-to-charge ratio of corresponding ms fragment ion is consistent with standard items, its abundance ratio compared with standard items deviation within ± 25% deviation.
8. adopt the quantitative measurement of external standard curve method, take concentration of standard solution as horizontal ordinate, quota ion peak area is ordinate separately, makes equation of linear regression, more quantitative with sample peak area and typical curve.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103926354A (en) * | 2014-05-06 | 2014-07-16 | 国家烟草质量监督检验中心 | Gas chromatography-mass spectrometry determination method for six phthalates in hot melt adhesive |
| CN106645512A (en) * | 2016-12-03 | 2017-05-10 | 南通博泰美术图案设计有限公司 | Rapid detection method |
| CN107917977A (en) * | 2017-12-12 | 2018-04-17 | 山东金胜粮油集团有限公司 | A kind of method for quickly detecting of grease plasticiser |
| US10518530B2 (en) | 2016-07-18 | 2019-12-31 | Hewlett-Packard Development Company, L.P. | Testing for wiping pre-treatment of print media |
Citations (3)
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| CN102620978A (en) * | 2012-04-09 | 2012-08-01 | 天津春发生物科技集团有限公司 | Matrix dispersion solid phase extraction method for detection of plasticizer in animal and vegetable oil samples |
| WO2013077985A1 (en) * | 2011-11-21 | 2013-05-30 | Waters Technologies Corporation | Screening for phthalates in food samples |
| RO129027A2 (en) * | 2012-05-14 | 2013-11-29 | Incdo-Inoe 2000, Filiala Institutul De Cercetări Pentru Instrumentaţie Analitică | Method of multi-residual determination of phthalates in food milk samples by ultrasonic extraction, micro-extraction in solid phase in headspace and gas chromatography coupled with mass spctrometry () |
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2014
- 2014-01-03 CN CN201410001568.5A patent/CN103760253A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013077985A1 (en) * | 2011-11-21 | 2013-05-30 | Waters Technologies Corporation | Screening for phthalates in food samples |
| CN102620978A (en) * | 2012-04-09 | 2012-08-01 | 天津春发生物科技集团有限公司 | Matrix dispersion solid phase extraction method for detection of plasticizer in animal and vegetable oil samples |
| RO129027A2 (en) * | 2012-05-14 | 2013-11-29 | Incdo-Inoe 2000, Filiala Institutul De Cercetări Pentru Instrumentaţie Analitică | Method of multi-residual determination of phthalates in food milk samples by ultrasonic extraction, micro-extraction in solid phase in headspace and gas chromatography coupled with mass spctrometry () |
Non-Patent Citations (2)
| Title |
|---|
| THOMAS WENZL: "Methods for the determination of phthalates in food", 《JRC EUROPEAN COMMISSION》 * |
| 中国国家标准化管理委员会: "食品中邻苯二甲酸酯的测定", 《中华人民共和国国家标准》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103926354A (en) * | 2014-05-06 | 2014-07-16 | 国家烟草质量监督检验中心 | Gas chromatography-mass spectrometry determination method for six phthalates in hot melt adhesive |
| US10518530B2 (en) | 2016-07-18 | 2019-12-31 | Hewlett-Packard Development Company, L.P. | Testing for wiping pre-treatment of print media |
| CN106645512A (en) * | 2016-12-03 | 2017-05-10 | 南通博泰美术图案设计有限公司 | Rapid detection method |
| CN107917977A (en) * | 2017-12-12 | 2018-04-17 | 山东金胜粮油集团有限公司 | A kind of method for quickly detecting of grease plasticiser |
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Application publication date: 20140430 |