CN102608225B - Determination method of harmful organic substance residue in toy sample - Google Patents
Determination method of harmful organic substance residue in toy sample Download PDFInfo
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Abstract
The invention adopts gas chromatography-mass spectrometry (GC-MS) to originally simultaneously determine residual contents of 9 kinds of organic substances in toy, including ethylene glycol monoethyl ether (EGEE), styrene, trimethylbenzene, isophorone, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, cyclohexanone, bis(2-methoxyethyl) ether, and nitrobenzene. Common detection device is adopted in the method. The method provided by the invention has the advantages of easy popularization, simultaneous detection to save time, improved efficiency, low cost, high detection rate and sensitivity, and high application value in toy production and quality detection.
Description
Technical field
The present invention relates to the residual assay method of a kind of harmful organic substance, particularly relate to a kind of 9 kinds of assay methods that harmful organic substance is residual in toy sample of simultaneously measuring.
Background technology
China is toys export big country at present, and nearly 2/3rds toy is at domestic product in the world.Current, guarantee that the quality safety of toy product becomes the key of China's toy industry development, and the chemical hazard being caused by toxic and harmful substance is a key factor that affects toy product quality safety.
9 kinds of materials such as the ethylene glycol monoethyl ether the present invention relates to are often used in the production run of toy.For example, styrene is widely used in as monomer toy materials such as manufacturing polystyrene (PS), acrylonitrile-butadiene-styrene terpolymer (ABS); The Chang Zuowei organic solvents such as ethylene glycol monoethyl ether, cyclohexanone, trimethylbenzene, isophorone are for the making of toy lacquer.According to the database of the authoritative organizations such as European Union's < < material and potpourri classification, packing and label rules > > (CLP) and Environmental Protection Agency (EPA) and international cancer research institution (IRAC), styrene, nitrobenzene, isophorone are considered to potential human carcinogen; Ethylene glycol monoethyl ether, 2-methoxyacetic acid ethyl ester, 2-ethoxy ethyl acetate, two (2-methoxy ethyls) ether is considered to have the material of genotoxicity, and cyclohexanone and trimethylbenzene also have certain toxicity on inhalation and acute toxicity.If these materials remain in toy product, Long Term Contact can cause harm in various degree to health.
Both at home and abroad for the study on determination method of 9 kinds of material residual quantities such as ethylene glycol monoethyl ether in product, what relate to is mainly the aspects such as food contact material, coating, water and aquatic products, air at present.Common detection method mainly contains vapor-phase chromatography (GC), GC-MS(gas chromatography-mass spectrography) (GC-MS), high performance liquid chromatography (HPLC) and photometry etc., and sample pre-treatments mode is mainly headspace sampling (HS), purge and trap, liquid-liquid extraction (SE), Solid-Phase Extraction (SPE), solid-phase microextraction (SPME) etc.And for the study on determination method of the material residual quantities such as ethylene glycol monoethyl ether in toy, in domestic and foreign literature and standard, report less.The present invention is intended to utilize gas chromatography-mass spectrum technology to set up a kind of assay method that simultaneously detects 9 kinds of organic substance residues amounts such as ethylene glycol monoethyl ether in toy, for formulating relevant limitation standard and Supervision Measures, provides technical support.
Summary of the invention
Technical matters solved by the invention is to provide a kind of assay method that simultaneously detects 9 kinds of organic substance residues amounts such as ethylene glycol monoethyl ether in toy sample.
In order to achieve the above object, the technical solution used in the present invention is: the residual assay method of harmful organic substance in toy sample, comprises the following steps:
(1) sample pre-treatments: toy sample samples after fragmentation, complete with organic solvent dissolution, add methyl alcohol and make plastic matrix precipitation, by the centrifugal rear solid-phase extraction column of crossing of supernatant, wash-out, eluent is transferred in nitrogen blowpipe after revolving steaming, blows to being less than 2mL at 40 ℃ with slow nitrogen stream, be settled to 2mL, extract is crossed after 0.2 μ m miillpore filter and measured for GC-MS;
(2) gas chromatography-mass spectrography is measured: adopt capillary chromatographic column, its injector temperature is 235 ℃, and mass scanning scope is 30m/z～140m/z, and ionization mode is EI, and ionizing energy is 70eV;
(3) drawing standard working curve: preparation standard working solution, under above-mentioned chromatographic condition, standard operation solution is measured from low to high successively by concentration, the peak area of the chromatographic peak that obtains of take is ordinate, the sample introduction concentration of each corresponding material is horizontal ordinate mapping, drawing standard working curve.
Assay method of the present invention, the organic solvent in wherein said step (1) is when toy sample is ABS plastic, solvent is acetone; When toy sample is PS plastics, solvent is methylene chloride; When toy sample is PVC plastics, solvent is tetrahydrofuran.
Assay method of the present invention, the solid-phase extraction column in wherein said step (1) is preferably Envi-carb graphitized carbon post.
Assay method of the present invention, chromatographic column adopting temperature programme in wherein said step (2): initial temperature is 40 ℃, keeps with 5 ℃/min speed, rising to 120 ℃ after 1min, then with 3 ℃/min speed, rises to 150 ℃, with 15 ℃/min speed, rise to 230 ℃, keep 5min.
Assay method of the present invention, the concentration of the standard operation solution in wherein said step (3) is: ethylene glycol monoethyl ether is 0.5mg/L～100mg/L; Styrene, trimethylbenzene and isophorone are 0.05mg/L～100mg/L; 2-methoxyacetic acid ethyl ester, 2-ethoxy ethyl acetate, cyclohexanone, two (2-methoxy ethyl) ether and nitrobenzene are 0.1mg/L～100mg/L.
The residual assay method of harmful organic substance in toy sample provided by the invention, measure first the residual quantity of ethylene glycol monoethyl ether in toy, styrene, trimethylbenzene, isophorone, 2-methoxyacetic acid ethyl ester, 2-ethoxy ethyl acetate, cyclohexanone, two (2-methoxy ethyl) ether and these 9 kinds of materials of nitrobenzene simultaneously, it adopts conventional pick-up unit, method is easy to popularize, and measuring 9 kinds of materials can save time simultaneously, raise the efficiency, reduce costs, recall rate is high, method is sensitive, aspect toy production and quality testing, has very high using value.
Accompanying drawing explanation
Fig. 1 is the typical chromatographic fractionation figure of 9 kinds of materials, wherein chromatographic peak: 1. ethylene glycol monoethyl ether; 2.2-methoxyacetic acid ethyl ester; 3. styrene; 4.2-ethoxy ethyl acetate; 5. cyclohexanone; 6. pair (2-methoxy ethyl) ether; 7. trimethylbenzene; 8. nitrobenzene; 9. isophorone.
Embodiment
For further illustrating the present invention, illustrate with the following Examples:
The assay method of simultaneously measuring the residual quantity of ethylene glycol monoethyl ether in toy, styrene, trimethylbenzene, isophorone, 2-methoxyacetic acid ethyl ester, 2-ethoxy ethyl acetate, cyclohexanone, two (2-methoxy ethyl) ether and these 9 kinds of materials of nitrobenzene, comprises the following steps:
1, sample pre-treatments
(1) toy sample is pulverized or shredded with scissors with cutting and grinding instrument, take 1.0g sample in 50mL conical flask, add 10mL coordinative solvent (ABS plastic acetone solution, PS plastics dissolve with methylene chloride, PVC plastics dissolve with tetrahydrofuran), sonic oscillation 15min.To be dissolved completely after, drip 10mL methyl alcohol, jolting, until plastic matrix precipitation completely, moves to centrifuge tube by solution, then uses 5mL washed with methanol conical flask, is then incorporated in centrifuge tube, centrifugal 10min under 10000r/min, 4 ℃ of conditions, gets settled solution stand-by.
(2) with 5mL methyl alcohol rinse Envi-carb graphitized carbon solid phase extraction column, the settled solution after centrifugal is crossed to post, 10mL methanol-eluted fractions, collects all post liquid of crossing in heart bottle.Solution is steamed to 5mL left and right at 10kPa, 30 ℃ of condition backspins, be transferred in the nitrogen blowpipe with scale, then use 1mL washed with methanol heart bottle, be incorporated in nitrogen blowpipe, at 40 ℃, with slow nitrogen stream, blow to being less than 2mL, be settled to 2mL, solution is crossed after 0.2 μ m miillpore filter and measured for GC-MS.
In pre-treatment step, toy matrix more complicated, the effect of Solid-Phase Extraction is mainly color and some other impurity of removing in plastic toys matrix.The present invention has investigated respectively 5 kinds of solid-phase extraction columns: Oasis HLB, the Sep-pakFlorisil of U.S. Waters company, Sep-pak NH2, the effect of extracting of the Chromabond Easy of German MN company and the Envi-carb graphitized carbon post of U.S. Supelco company.First each extraction column is activated with methyl alcohol, the simulation solution that is then 10mg/L by 25mL concentration, by solid-phase extraction column, is used methanol-eluted fractions.Collect all post solution of crossing, for GC-MS, measure.Result shows, Envi-carb graphitized carbon post is best to the clean-up effect of plastic toys matrix, uses 10ml methanol-eluted fractions, and wash-out object can be retained in the impurity such as color on post again completely.
2, Gas Chromatography-Mass Spectrometry condition
A. capillary chromatographic column: DB-624 quartz capillary column: 60m * 0.25mm i.d., 1.4 μ m, or equivalent person;
B. temperature programme: initial temperature is 40 ℃, keeps with 5 ℃/min speed, rising to 120 ℃ after 1min, then with 3 ℃/min speed, rises to 150 ℃, with 15 ℃/min speed, rises to 230 ℃, keeps 5min;
C. carrier gas: high-pure helium, flow velocity is 1.0mL/min;
D. injector temperature: 235 ℃; Sample introduction pattern: split sampling, split ratio 10: 1;
E. detecting device: mass selective detector (MSD); Mass scanning scope: 30m/z～140m/z;
G. interface temperature: 250 ℃;
H. ionization mode: EI; Ionizing energy: 70eV;
I. monitoring mode: SIM;
Typical chromatographic fractionation figure as shown in Figure 1.The characteristic ion of each material is as shown in the table:
The characteristic ion that 9 kinds of material titles that relate in table 1 the present invention and mensuration thereof are used
| Title | CAS | Characteristic ion (is quota ion with *) |
| Ethylene glycol monoethyl ether | 110-80-5 | 31/45/59* |
| 2-methoxyacetic acid ethyl ester | 110-49-6 | 43*/45/48 |
| Styrene | 100-42-5 | 78/103/104* |
| 2-ethoxy ethyl acetate | 111-15-9 | 43*/59/72 |
| Cyclohexanone | 108-94-1 | 42/55*/98 |
| Two (2-methoxy ethyl) ether | 111-96-6 | 45/58/59* |
| Trimethylbenzene | 108-67-8 | 105*/119/120 |
| Nitrobenzene | 98-95-3 | 51/77*/123 |
| Isophorone | 78-59-1 | 54/82*/138 |
3, the preparation of standard solution and standard working curve
Standard inventory solution: take the standard items 0.1g (being accurate to 1mg) of each material to the brown volumetric flask of 100ml, methanol constant volume, obtaining concentration is the standard inventory solution of 1000mg/L.
Standard operation solution: draw above standard inventory solution appropriate, be diluted to the working solution of desired concn with methyl alcohol, for ethylene glycol monoethyl ether, the concentration range of working solution is 0.5mg/L～100mg/L; For styrene, trimethylbenzene and isophorone, the concentration range of working solution is 0.05mg/L～100mg/L; For 2-methoxyacetic acid ethyl ester, 2-ethoxy ethyl acetate, cyclohexanone, two (2-methoxy ethyl) ether and nitrobenzene, the concentration range of working solution is 0.1mg/L～100mg/L.Be placed in 4 ℃ and keep in Dark Place, stand-by.
Under the chromatographic condition of setting, standard operation solution to be measured from low to high successively by concentration, the peak area of the chromatographic peak that obtains of take is ordinate, the sample introduction concentration of each corresponding material is horizontal ordinate mapping, drawing standard working curve.Result shows, each material is in its range of linearity, and concentration value and peak area have good linear relationship, and linearly dependent coefficient is all greater than 0.9995.
The present invention using response signal while being greater than 10 times of noises corresponding content of material as quantitative limit, determine that the quantitative limit of each material is all less than 1.0mg/kg.Result is as shown in table 2:
Typical linear equation is also as shown in table 2.
The quantitative limit of the range of linearity, linear equation, related coefficient and the method for table 210 kind of material
4, the recovery of method and precision
We have set 3 for every kind of material and have added concentration, by the determined experiment condition of this method, each is added to concentration and repeat 6 tests.Found that, except trimethylbenzene, the average recovery rate of material is between 70%～94%, and the trimethylbenzene recovery is lower, and reason may be that the saturated vapour pressure of trimethylbenzene is larger, loses more in revolving steaming process.Method for the RSD of different material between 2.8%～6.5%.Because styrene is present in the plastics such as ABS, PS as monomer, content is relatively large, and we do not find blank sample, does not therefore carry out its determination of recovery rates test.DCO the results are shown in table 3.
The different recovery and precision (n=6) of adding concentration material in table 3 toy
5, the mensuration of actual toy sample
Apply this method, buy from the market 7 kinds of ABS material toy samples are carried out to the mensuration of above-mentioned 9 kinds of organic substance residues amounts.Found that, in 7 kinds of toys, all detect styrene, content is respectively 347mg/kg, 81mg/kg, 582mg/kg, 325mg/kg, 127mg/kg, 164mg/kg and 245mg/kg, and all the other 8 kinds of materials do not detect in these 7 kinds of toy samples.
Above-described embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention, all should fall in the definite protection domain of claims of the present invention.
Claims (2)
1. the assay method of simultaneously measuring the residual quantity of ethylene glycol monoethyl ether in toy, styrene, trimethylbenzene, isophorone, 2-methoxyacetic acid ethyl ester, 2-ethoxy ethyl acetate, cyclohexanone, two (2-methoxy ethyl) ether and these 9 kinds of materials of nitrobenzene, is characterized in that: comprise the following steps:
(1) sample pre-treatments: toy sample samples after fragmentation, complete with organic solvent dissolution, add methyl alcohol and make plastic matrix precipitation, by the centrifugal rear solid-phase extraction column of crossing of supernatant, wash-out, eluent is transferred in nitrogen blowpipe after revolving steaming, at 40 ℃, with slow nitrogen stream, blow to being less than 2mL, be settled to 2mL, obtain extract, extract is crossed after 0.2 μ m miillpore filter for Gas Chromatography-Mass Spectrometry; Described solid-phase extraction column is Envi-carb graphitized carbon post;
(2) gas chromatography-mass spectrography is measured: adopt capillary chromatographic column, its injector temperature is 235 ℃, and mass scanning scope is 30m/z～140m/z, and ionization mode is EI, and ionizing energy is 70eV;
Chromatographic column adopting temperature programme: initial temperature is 40 ℃, keeps with 5 ℃/min speed, rising to 120 ℃ after 1min, then with 3 ℃/min speed, rises to 150 ℃, with 15 ℃/min speed, rises to 230 ℃, keeps 5min;
(3) drawing standard working curve: preparation standard working solution, under above-mentioned chromatographic condition, standard operation solution is measured from low to high successively by concentration, the peak area of the chromatographic peak that obtains of take is ordinate, the sample introduction concentration of each corresponding material is horizontal ordinate mapping, drawing standard working curve;
The concentration of standard operation solution is: ethylene glycol monoethyl ether is 0.5mg/L～100mg/L; Styrene, trimethylbenzene and isophorone are 0.05mg/L～100mg/L; 2-methoxyacetic acid ethyl ester, 2-ethoxy ethyl acetate, cyclohexanone, two (2-methoxy ethyl) ether and nitrobenzene are 0.1mg/L～100mg/L.
2. assay method according to claim 1, is characterized in that: the organic solvent in described step (1) is when toy sample is ABS plastic, and solvent is acetone; When toy sample is PS plastics, solvent is methylene chloride; When toy sample is PVC plastics, solvent is tetrahydrofuran.
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| CN102998387B (en) * | 2012-11-23 | 2014-04-09 | 江苏中烟工业有限责任公司 | Method for determining ethylene glycol monomethyl ether, glycol ether, ethylene glycol ether acetate, glycol and diglycol in food wrap paper |
| CN103308358B (en) * | 2013-04-20 | 2016-05-04 | 东莞龙昌智能技术研究院 | The preparation method of the Analysis of Heavy Metal standard substance of a kind of modified polyvinyl chloride and ABS mixture |
| CN103267809A (en) * | 2013-04-22 | 2013-08-28 | 深圳市谱尼测试科技有限公司 | Gas chromatography method for detecting methoxy acetate in electronic products |
| CN104181261A (en) * | 2013-05-28 | 2014-12-03 | 张莉 | Improvement of method for ultrasonic extraction of nitrobenzene compounds in animal sample |
| CN103399111B (en) * | 2013-07-10 | 2015-07-15 | 江苏中烟工业有限责任公司 | Method for selectively measuring ethylene glycol monoethyl ether acetate in dry food packaging paper based on headspace-gas chromatography/mass spectrometry |
| CN106383179B (en) * | 2016-08-19 | 2019-04-02 | 延锋安道拓座椅有限公司 | A method of detection low concentration of styrene |
| CN108627592B (en) * | 2017-03-24 | 2021-05-04 | 上海安谱实验科技股份有限公司 | Method for extracting polycyclic aromatic hydrocarbon from ABS, PVC, PP and PS products |
| CN108037223A (en) * | 2017-12-13 | 2018-05-15 | 中山永恒检测科技有限公司 | The detection method of bisphenol-A in a kind of paint |
| CN109541083B (en) * | 2019-01-30 | 2022-05-10 | 广州质量监督检测研究院 | Method for detecting volatile odor substances in polyvinyl chloride product |
| CN112379023B (en) * | 2020-11-18 | 2021-12-07 | 江南大学 | Method for detecting 8 organic residues in ion exchange resin by headspace gas phase method |
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