CN104950061A - Quick detection method - Google Patents
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- CN104950061A CN104950061A CN201510325459.3A CN201510325459A CN104950061A CN 104950061 A CN104950061 A CN 104950061A CN 201510325459 A CN201510325459 A CN 201510325459A CN 104950061 A CN104950061 A CN 104950061A
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Abstract
The invention relates to a quick detection method, and discloses a quick testing method for a plasticizer. The quick detection method comprises the following steps: preparation of a plasticizer mixed standard solution, preparation of a plasticizer mixed standard use solution, sample treating, and sampling testing; the purpose of quick detection is achieved by increasing the use amount of an extracting agent and conducting extraction and concentration to shorten the sample pretreatment time. The sample treating time of the quick detection method is far shorter than the sample processing time of an international standard method, and the quick detection method is suitable for being used when a large amount of samples are screened in a primary laboratory. The current situations of troublesome sample pretreatment in an experiment, time and labor consuming and high detection cost are changed.
Description
Technical field
The present invention relates to a kind of detection method of plasticiser, particularly relate to a kind of method that plasticiser shortening the sample pretreatment time detects fast.
Background technology
Plasticiser is also plastifier, can reduce high polymer material glass transition temperature and improve the auxiliary agent of plasticity.Industrially, plasticiser be plasthetics shaping time additive, the much over one hundred items of plasticiser kind, but namely use the most general be the compound that a group is called phthalate, such as: DEHP, DINP, DBP, DIDP, BBP, DNOP, DEP and DMP.To the query of this type of plasticiser security, mainly come from its oestrogen-like hormone effect, male endocrine may be caused disorderly, cause sperm quantity to reduce, degradation under fecundity.Therefore the absorption of plasticiser can cause huge injury to health, so the Fast Detection Technique of plasticiser is for safeguarding that human security is extremely important.
At present, the sample-pretreating method that the detection of " plasticiser " is conventional first adopts liquid-liquid extraction, then through SPE post and gel permeation chromatograph (GPC) purification; Instrument analytical method has GC method, HPLC method, GC-MS method.Required by existing detection technique laboratory sample pre-service trouble, not only time-consuming, effort and testing cost high, can not 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 sample processing time, improves the method for quick of detection efficiency.
For solving the problems of the technologies described above, the technical solution used in the present invention is: method for quick, the preparation of plasticiser mixed standard solution, sample preparation and sample determination step, its innovative point is: in sample handling procedure, sample is carried out different process respectively according to not containing oil sample, pure oil sample and containing oil sample three class.
Further, sample detection is specially:
(1) sample containing carbon dioxide gas needs first removing carbon dioxide, adds normal hexane 12mL, ultrasonic extraction 5min, and stratification, gets supernatant and measure;
(2) grease sample volume ratio be 1: 1 ethyl acetate and cyclohexane mixed liquor be settled to 50mL, vortex mixed 5min, after 0.45 μm of membrane filtration, filtrate concentrated by rotary evaporation, to 2.0mL, measures;
(3) oil-containing sample first adds 20mL sherwood oil vortex mixed 2min, petroleum ether layer is extracted after leaving standstill, use 12mL petroleum ether layer repeated washing triangular flask again, carry out three times altogether, merge petroleum ether layer, be evaporated to dry, with volume ratio be 1: 1 ethyl acetate and cyclohexane mixed liquor be settled to 50mL, vortex mixed 5min, after 0.45 μm of membrane filtration, filtrate concentrated by rotary evaporation, to 2.0mL, measures.
Further, in described step (1) when layered effect is bad, with the centrifugation 5min of 5500r/min.
Further, described normal hexane, ethyl acetate, cyclohexane are all the residual level reagent of agriculture, sherwood oil to be boiling range the be sherwood oil of 35 DEG C ~ 55 DEG C.
Further, plasticiser mixed standard solution is prepared: be the storing solution of 100mg/L by hybrid standard product normal hexane constant volume, preserves, be then diluted to standard series point with normal hexane stand-by under 4 DEG C ± 1 DEG C condition.
Further, use gas chromatograph-mass spectrometer (GCMS) in sample determination process, adopt the method for split sampling, described condition determination is:
A) gas phase condition:
Chromatographic column: HP-5MS capillary chromatographic column (30m × 0.25mm × 0.25 μm); Injector temperature: 250 DEG C; Split sampling, split ratio 5: 1; Carrier gas: helium, purity 99.999%; Column temperature: 55 DEG C, keeps 1min with 20 DEG C/min ramp to 220 DEG C after keeping 1min, then is warming up to 280 DEG C with 5 DEG C/min, keep 5min; Flow rate of carrier gas: 1.0mL/min; Sample size: 1 μ L;
B) Mass Spectrometry Conditions: electron impact ion source; Electron-multiplier voltage 1301ev; Ionization voltage 70ev; Ion source temperature 235 DEG C; Quadrupole rod temperature 150 DEG C; Interface temperature 280 DEG C; 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 determination sample composition, adopt external standard curve standard measure, concrete is: sample liquid to be measured occurs at identical retention time place with standard items Selective ion mode chromatographic peak, and the mass-to-charge ratio of corresponding mass spectrometric fragment ion is consistent with standard items, its abundance ratio compared with standard items deviation within ± 25% deviation.Adopt external standard curve standard measure to measure, take concentration of standard solution as horizontal ordinate, respective quota ion peak area is ordinate, makes equation of linear regression, more quantitative with typical curve with sample peak area.
Beneficial effect: what the present invention adopted is that the mode that extraction concentrates carries out sample pre-treatments, in the sample to which by increasing the amount of extraction agent normal hexane to shorten extraction time.For containing oils sample, do not need gel chromatography device to purify, sample processing time, far less than the national standard method processing time, is adapted at using when laboratories does the screening of a large amount of sample.To change in experiment sample pretreatment trouble, 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 reagent of agriculture, and it is pure that other agents useful for same such as sherwood oil (boiling range 35 DEG C ~ 55 DEG C), acetone are analysis.
Experimental water is the ultrapure water of Mi Libo ultrapure water instrument.
2) 16 kinds of plasticisers and phthalic ester hybrid standard product are purchased from Town in Shanghai spectrum company
Plasticiser mixed standard solution: be the storing solution of 100mg/L by hybrid standard product normal hexane constant volume, keeps in Dark Place in 4 DEG C of refrigerators.
3) plasticiser hybrid standard uses liquid: standard reserving solution normal hexane is diluted to concentration be 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) (Agilent company of the U.S.);
2) utility appliance: BIOFUGE STRATOS high-speed refrigerated centrifuge (Thermo Fisher company of the U.S.); 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, add normal hexane 12mL, ultrasonic extraction 5min, stratification (layered effect is bad makes the centrifugal 5min of 5500r/min), gets supernatant and measures, do reagent blank simultaneously;
2) sample determination:
A) gas phase condition:
Chromatographic column: HP-5MS capillary chromatographic column (30m × 0.25mm × 0.25 μm)
Injector temperature: 250 DEG C;
Split sampling, split ratio 5: 1;
Carrier gas: helium, purity 99.999%;
Column temperature: 55 DEG C, keeps 1min with 20 DEG C/min ramp to 220 DEG C after keeping 1min, then is warming up to 280 DEG C with 5 DEG C/min, keep 5min;
Flow rate of carrier gas: 1.0mL/min;
Sample size: 1 μ L;
B) Mass Spectrometry Conditions: electron impact ion source; Electron-multiplier voltage 1301ev; Ionization voltage 70ev; Ion source temperature 235 DEG C; Quadrupole rod temperature 150 DEG C; Interface temperature 280 DEG C; 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 occurs identical retention time place (± 0.5%) with standard items Selective ion mode chromatographic peak, and the mass-to-charge ratio of corresponding mass spectrometric fragment ion is consistent with standard items, its abundance ratio compared with standard items deviation within ± 25% deviation.Adopt external standard curve standard measure to measure, take concentration of standard solution as horizontal ordinate, respective quota ion peak area is ordinate, makes equation of linear regression, more quantitative with typical curve with sample peak area.
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 μm of membrane filtration, filtrate concentrated by rotary evaporation is to 2.0mL, measure, 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, petroleum ether layer is extracted after leaving standstill, use 12mL petroleum ether layer repeated washing triangular flask again, carry out three times altogether, merge petroleum ether layer, be evaporated to dry, with ethyl acetate: cyclohexane (V/V=1) is settled to 50mL, vortex mixed 5min, after 0.45 μm of membrane filtration, filtrate concentrated by rotary evaporation is to 2.0mL, measure, assay method with embodiment 1, the present embodiment recovery of standard addition 86.9% ~ 106.2%.
Claims (7)
1. method for quick, the preparation of plasticiser mixed standard solution, sample preparation and sample determination step, is characterized in that: in sample handling procedure, sample is carried out different process respectively according to not containing oil sample, pure oil sample and containing oil sample three class.
2. method for quick according to claim 1, is characterized in that: sample detection is specially:
(1) sample containing carbon dioxide gas needs first removing carbon dioxide, adds normal hexane 12mL, ultrasonic extraction 5min, and stratification, gets supernatant and measure;
(2) grease sample volume ratio be 1: 1 ethyl acetate and cyclohexane mixed liquor be settled to 50mL, vortex mixed 5min, after 0.45 μm of membrane filtration, filtrate concentrated by rotary evaporation, to 2.0mL, measures;
(3) oil-containing sample first adds 20mL sherwood oil vortex mixed 2min, petroleum ether layer is extracted after leaving standstill, use 12mL petroleum ether layer repeated washing triangular flask again, carry out three times altogether, merge petroleum ether layer, be evaporated to dry, with volume ratio be 1: 1 ethyl acetate and cyclohexane mixed liquor be settled to 50mL, vortex mixed 5min, after 0.45 μm of membrane filtration, filtrate concentrated by rotary evaporation, to 2.0mL, measures.
3. method for quick according to claim 2, is characterized in that: in described step (1) when layered effect is bad, with the centrifugation 5min of 5500r/min.
4. method for quick according to claim 2, is characterized in that: described normal hexane, ethyl acetate, cyclohexane are all the residual level reagent of agriculture, sherwood oil to be boiling range the be sherwood oil of 35 DEG C ~ 55 DEG C.
5. method for quick according to claim 1, it is characterized in that: plasticiser mixed standard solution is prepared: be the storing solution of 100mg/L by hybrid standard product normal hexane constant volume, preserve under 4 DEG C ± 1 DEG C condition, be then diluted to standard series point with normal hexane stand-by.
6. method for quick according to claim 1, is characterized in that: use gas chromatograph-mass spectrometer (GCMS) in sample determination process, and adopt the method for split sampling, described condition determination is:
A) gas phase condition:
Chromatographic column: HP-5MS capillary chromatographic column (30m × 0.25mm × 0.25 μm); Injector temperature: 250 DEG C; Split sampling, split ratio 5: 1; Carrier gas: helium, purity 99.999%; Column temperature: 55 DEG C, keeps 1min with 20 DEG C/min ramp to 220 DEG C after keeping 1min, then is warming up to 280 DEG C with 5 DEG C/min, keep 5min; Flow rate of carrier gas: 1.0mL/min; Sample size: 1 μ L;
B) Mass Spectrometry Conditions: electron impact ion source; Electron-multiplier voltage 1301ev; Ionization voltage 70ev; Ion source temperature 235 DEG C; Quadrupole rod temperature 150 DEG C; Interface temperature 280 DEG C; SIM/ full scan (SCAN) drainage pattern, quality of scanning scope: m/z 30 ~ 350; Solvent delay time 5min; Sample frequency 2.
7. 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 determination sample composition, adopt external standard curve standard measure, concrete is: sample liquid to be measured occurs at identical retention time place with standard items Selective ion mode chromatographic peak, and the mass-to-charge ratio of corresponding mass spectrometric fragment ion is consistent with standard items, its abundance ratio compared with standard items deviation within ± 25% deviation.Adopt external standard curve standard measure to measure, take concentration of standard solution as horizontal ordinate, respective quota ion peak area is ordinate, makes equation of linear regression, more quantitative with typical curve with sample peak area.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108062456A (en) * | 2017-12-12 | 2018-05-22 | 湖南省检验检疫科学技术研究院 | The identification method of perfume ingredient in a kind of 3T2M1MS databases and its method for building up and tealeaves |
| CN108088924A (en) * | 2017-12-13 | 2018-05-29 | 三明出入境检验检疫局综合技术服务中心 | The rapid detection method of fluorescent whitening agent PF in a kind of plastics package white wine |
-
2015
- 2015-06-05 CN CN201510325459.3A patent/CN104950061A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 丁红梅 等: "食品中塑化剂的快速检测方法研究", 《粮油食品科技》 * |
| 杨润 等: "食品中邻苯二甲酸酯类化合物残留检测与方法探讨", 《江苏预防医学》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108062456A (en) * | 2017-12-12 | 2018-05-22 | 湖南省检验检疫科学技术研究院 | The identification method of perfume ingredient in a kind of 3T2M1MS databases and its method for building up and tealeaves |
| CN108088924A (en) * | 2017-12-13 | 2018-05-29 | 三明出入境检验检疫局综合技术服务中心 | The rapid detection method of fluorescent whitening agent PF in a kind of plastics package white wine |
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