CN103983717A - Method for quickly measuring decomposable carcinogenic aromatic amine dye in textile - Google Patents
Method for quickly measuring decomposable carcinogenic aromatic amine dye in textile Download PDFInfo
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- CN103983717A CN103983717A CN201410217526.5A CN201410217526A CN103983717A CN 103983717 A CN103983717 A CN 103983717A CN 201410217526 A CN201410217526 A CN 201410217526A CN 103983717 A CN103983717 A CN 103983717A
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Abstract
The invention relates to a method for quickly measuring a decomposable carcinogenic aromatic amine dye in a textile, and aims to provide a detection method which is easy to operate and low in cost. According to the technical scheme, the method for quickly measuring the decomposable carcinogenic aromatic amine dye in the textile comprises the following steps of (1) cutting a textile sample to be detected into pieces, putting the pieces into a reactor with a plug, adding a preheated citrate buffering solution, and putting the container into a water bath for heat preservation after the reactor is shaken and the materials are mixed; (2) closing the reactor for shaking mixing after sodium hydrosulfite solution is added, then putting the reactor with the plug into the water bath for heat preservation, and cooling to room temperature within 2min; (3) transferring a certain amount of sample liquid into a centrifugal pipe with a plug from the container, and adding a certain amount of acetonitrile for uniform mixing; (4) weighing a certain amount of a hydrophobic solvent, injecting the hydrophobic solvent into a mixed solution obtained in the step (3), and performing centrifugal treatment after shaking or vortex mixing is performed; and (5)taking a certain amount of centrifugated supernate for liquid or gas chromatographic analysis.
Description
Technical field
The present invention relates to a kind of method of utilizing the solvent-induced extraction Fast Measurement textile that is separated can decompose carcinogenic aromatic amine dyestuff.
Background technology
Early stage research and clinical testing confirmation, some azo dyes can be take different approaches deoxidization, degradation as human body or animal being had to the aromatic amine material of potential carcinogenicity in environment.To decomposing the detection of carcinogenic aromatic amine dyestuff, become one of most important quality control project at present domestic and international textils and clothing trade, routine testing sample size is very huge.
To what can decompose in textile that the mensuration of carcinogenic aromatic amine dyestuff adopts, be at present traditional liquid-liquid extraction method, specifically the aromatic amine in water extracted in organic solvent, after concentrating constant volume, carry out instrumental analysis.Whole pretreatment process is complicated, and not only speed is slow, efficiency is lower, and the reappearance of testing result is not good; In addition extraction process need to be used disposable zeyssatite pillar and a large amount of organic solvent, and testing cost is high and unfriendly to environment, and operating personnel's health is had a certain impact.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned background technology, provide a kind of and operate the detection method easier, cost is lower than act.std method.
Technical scheme provided by the invention is: a kind of can decompose carcinogenic aromatic amine dyestuff in Fast Measurement textile method, carry out according to the following steps:
1) put into tool plug reactor after 1.0g textile sample to be checked is shredded to (being conventionally less than 5mm * 5mm), then add 17mL to be preheating to the citrate buffer of 70 ± 2 ℃, jolting mixes to be placed in 70 ± 2 ℃ of water-baths and is incubated 30 ± 5min;
2) adding 3mL content is that after 200mg/L hydrosulfurous acid sodium solution, airtight jolting mixes, then tool plug reactor is incubated to 30 ± 5min in 70 ± 2 ℃ of water-baths; Then in 2min, be cooled to room temperature;
3) in container, pipette a certain amount of sample liquid in tool plug centrifuge tube, add a certain amount of acetonitrile to mix simultaneously, the volume ratio of sample liquid and acetonitrile is 3.6-1.5: 1;
4) pipette a certain amount of hydrophobic solvent implantation step 3) mixed liquor in, jolting or vortex carry out centrifugal treating after mixing, the volume ratio of hydrophobic solvent and acetonitrile is 0.05-0.24: 1;
5) get step 4) centrifugal rear a certain amount of supernatant, upper machine carries out liquid phase or gas chromatographic analysis.
Step 3) the sample liquid acetonitrile volume ratio long-pending and that add in is 1.2-1.9: 1.
Step 4) the hydrophobic organic solvent volume adding in and the volume ratio of acetonitrile are 0.07-0.14: 1.
Step 4) described hydrophobic solvent is methenyl choloride or chlorobenzene or toluene or 1-hexyl-3-methylimidazole hexafluorophosphate or 1-octyl group-3-methylimidazole hexafluorophosphate.
The principle that utilization of the present invention adds micro-hydrophobic solvent can impel acetonitrile and water two to be separated in the system of dissolving each other of acetonitrile and water, adopting acetonitrile is the aromatic amine in extractant aqueous phase extracted, two be separated after, organic phase can be directly used in stratographic analysis.Not only accuracy of detection can meet routine testing requirement, operation steps is simplified, and be only 1/2nd of existing detection method detection time, and inspection cost is reduced (being reduced to below 1/5th) greatly, and matrix interference is less, more friendly to environment; Can be widely used in the routine check of this project of textile laboratory.
Accompanying drawing explanation
Fig. 1 is the contrast colors spectrogram that embodiment 1 adopts the present invention and adopts national standard method to detect.
Embodiment
Detection method provided by the invention, mainly to optimize pretreatment process, specifically adopting acetonitrile is the aromatic amine in extractant aqueous phase extracted, after adding micro-hydrophobic solvent that acetonitrile and water two are separated, pipettes a certain amount of upper organic phase and is directly used in stratographic analysis.
With existing detection method comparison, the advantage possessing is:
1, with acetonitrile, replacing hydrophobic organic solvent is the aromatic amine in extractant aqueous phase extracted, can be directly used in stratographic analysis, and single extraction efficiency is higher.
2, one is got and concentrated in to treasury, avoided rotary evaporation concentration process, and operating process is more simple and quick, and cost is lower.
Embodiment 1
In silk muffler, forbid the detection of azo dyes
1, running program:
Get silk muffler sample that 1.0g shreds in 65mL tool plug reactor, add 17mL to be preheating to the citrate buffer of (70 ± 2) ℃, jolting is placed in (70 ± 2) ℃ water-bath and is incubated 30min.Add airtight jolting immediately after 3.0mL200mg/L hydrosulfurous acid sodium solution, then reactor is incubated to 30min in (70 ± 2) ℃ water-bath.After taking out, in 2min, be cooled to room temperature; Then pipette 3.0mL sample liquid in 15mL tool plug taper centrifuge tube, add 1.4mL acetonitrile, with the light jolting of have gentle hands, make to mix, then with micro syringe, pipette 120 μ L methenyl cholorides and inject acetonitrile/water mixed liquor.Centrifuge tube is mixed on vortex mixer to 1min, then with the centrifugal 1min of speed of 4000rpm.With micro syringe, draw a certain amount of supernatant liquor in the sample bottle with taper interpolation pipe, for liquid-phase chromatographic analysis.
2, liquid phase chromatogram condition
Instrument: Waters2695, is furnished with 2996 diode array detectors;
Chromatographic column:
post (250mm * 4.6mm, 5 μ m);
Mobile phase A: methyl alcohol, Mobile phase B: 0.575g ammonium dihydrogen phosphate (ADP)+0.7g sodium hydrogen phosphate, is dissolved in 1000mL ultrapure water;
Gradient: by 15% mobile phase A and 85% Mobile phase B, then linearly change 80% mobile phase A and 20% Mobile phase B in 45min when initial, keep 5min.
Flow: 0.8mL/min;
Sample size: 20 μ L;
Column temperature: 40 ℃.
Detect wavelength: 240nm, 280nm, 305nm.
3, testing result: detect biphenylamine, this method quantitative result is 475mg/kg, adopting the quantitative result of national standard method GB/T17592-2011 is 440mg/kg; Correlation ratio reaches more than 92%.
4, Fig. 1 is the contrast colors spectrogram that sample adopts this method and employing national standard method.
In figure, be labeled as:
1, biphenylamine
A: adopt national standard method GB/T17592-2011 to detect chromatogram; B: adopt the inventive method to detect chromatogram.
Embodiment 2
In jeans, forbid the detection of azo dyes
1, running program:
Get jeans fabric that 1.0g shreds in 65mL tool plug reactor, add 17mL to be preheating to the citrate buffer of (70 ± 2) ℃, firmly jolting is placed in (70 ± 2) ℃ water-bath and is incubated 30min.Adding 3.0mL concentration is airtight jolting immediately after 200mg/L hydrosulfurous acid sodium solution, then reactor is incubated to 30min in (70 ± 2) ℃ water-bath.After taking-up, be cooled to room temperature; Then pipette 2.0mL sample liquid in 10mL tool plug taper centrifuge tube, add 1.0mL acetonitrile, with the light jolting of have gentle hands, make to mix, then with micro syringe, pipette 80 μ L methenyl cholorides and inject acetonitrile/water mixed liquor.Centrifuge tube is mixed on vortex mixer to 1min, then with the centrifugal 1min of speed of 4000rpm.With micro syringe, draw 1 μ L upper organic phase and be directly used in gas chromatography-mass spectrometry analysis.
2, instrumental analysis condition
Instrument: Thermo Trace GC Ultra/DSQ II MSD gas chromatograph-mass spectrometer (GCMS);
Chromatographic column: DB-5MS (30m * 0.25mm * 0.25 μ m);
Injector temperature: 250 ℃;
Mass spectrometer interface temperature: 280 ℃;
Column temperature: 60 ℃ (1min)
10 ℃/min190 ℃
3 ℃/min235 ℃
10 ℃/min280 ℃ (5min)
Carrier gas and carrier gas flux: helium (purity >99.999%), 1.0mL/min;
Ion source temperature: 250 ℃;
Scan mode: full scan;
Mass scanning scope: 35-350amu.
3, testing result: detect 3,3 '-dimethoxy benzidine 32mg/kg; As a comparison, adopt 3 of the method EN14362.1-2012 of European Union, it is 30mg/kg that 3 '-dimethoxy benzidine detects result.
Embodiment 3
In knitting cotton, forbid the detection of azo dyes
1, running program:
Get cotton sample that 1.0g shreds in 65mL tool plug reactor, add 17mL to be preheating to the citrate buffer of 70 ± 2 ℃, firmly jolting is placed in (70 ± 2) ℃ water-bath and is incubated 30min; Add airtight jolting immediately after 3.0mL200mg/L hydrosulfurous acid sodium solution, then reactor is incubated to 30min in (70 ± 2) ℃ water-bath; After taking out, in 2min, be cooled to room temperature.Then pipette 3.0mL sample liquid in 10mL tool plug taper centrifuge tube, add 1.4mL acetonitrile, with the light jolting of have gentle hands, make to mix, then with micro syringe, pipette 160 μ L1-hexyl-3-methylimidazole hexafluorophosphates and inject acetonitrile/water mixed liquor; Centrifuge tube is mixed on vortex mixer to 1min, then with the centrifugal 1min of speed of 4000rpm.With micro syringe, draw a certain amount of supernatant liquor in the sample bottle with taper interpolation pipe, on liquid chromatograph, analyze.
2, liquid phase chromatogram condition
Instrument: Waters2695, is furnished with 2996 diode array detectors;
Chromatographic column:
post (250mm * 4.6mm, 5 μ m);
Mobile phase A: methyl alcohol, Mobile phase B: 0.01mol/L sodium acetate (pH=3.6);
Gradient: by 15% mobile phase A and 85% Mobile phase B, then linearly change 80% mobile phase A and 20% Mobile phase B in 45min when initial, keep 5min.
Flow: 0.8mL/min;
Sample size: 20 μ L;
Column temperature: 40 ℃.
Detect wavelength: 240nm, 280nm, 305nm.
3, testing result: detect 2-naphthylamines 18mg/kg; As a comparison, adopting the 2-naphthylamines of national standard method GB/T17592-2011 to detect result is 15mg/kg.
Embodiment 4
In sheet, forbid the detection of azo dyes
1, running program:
Get sheet sample that 1.0g shreds in 65mL tool plug reactor, add 17mL to be preheating to the citrate buffer of (70 ± 2) ℃, firmly jolting is placed in (70 ± 2) ℃ water-bath and is incubated 30min.Add airtight jolting immediately after 3.0mL200mg/L hydrosulfurous acid sodium solution, then reactor is incubated to 30min in (70 ± 2) ℃ water-bath.After taking-up, be cooled to room temperature; Then pipette 3.0mL sample liquid in 10mL tool plug taper centrifuge tube, add 1.4mL acetonitrile, with the light jolting of have gentle hands, make to mix, then with micro syringe, pipette 100 μ L chlorobenzenes and inject acetonitrile/water mixed liquor.Centrifuge tube is mixed on vortex mixer to 1min, then with the centrifugal 1min of speed of 4000rpm.With micro syringe, draw 1 μ L upper organic phase and be directly used in gas chromatography-mass spectrometry analysis.
2, instrumental analysis condition
Instrument: Thermo Trace GC Ultra/DSQ II MSD gas chromatograph-mass spectrometer (GCMS);
Chromatographic column: DB-5MS (30m * 0.25mm * 0.25 μ m);
Injector temperature: 250 ℃;
Mass spectrometer interface temperature: 280 ℃;
Column temperature: 60 ℃ (1min)
10 ℃/min190 ℃
3 ℃/min235 ℃
10 ℃/min280 ℃ (5min)
Carrier gas and carrier gas flux: helium (purity >99.999%), 1.0mL/min;
Ion source temperature: 250 ℃;
Scan mode: full scan;
Mass scanning scope: 35-350amu.
3, testing result: detect biphenylamine 89mg/kg; As a comparison, adopting the biphenylamine of national standard method GB/T17592-2011 to detect result is 78mg/kg.
Claims (4)
1. the method that can decompose carcinogenic aromatic amine dyestuff in Fast Measurement textile, carry out according to the following steps:
1) put into tool plug reactor after 1.0g textile sample to be checked is shredded, then add 17mL to be preheating to the citrate buffer of 70 ± 2 ℃, jolting is placed in 70 ± 2 ℃ of water-baths and is incubated 30 ± 5min;
2) add airtight jolting immediately after 3mL200mg/L hydrosulfurous acid sodium solution, then reactor is incubated to 30 ± 5min in 70 ± 2 ℃ of water-baths; Then be cooled to room temperature;
3) in container, pipette a certain amount of sample liquid in tool plug centrifuge tube, add a certain amount of acetonitrile to mix simultaneously, the volume ratio of sample liquid and acetonitrile is 3.6-1.5: 1;
4) pipette a certain amount of hydrophobic solvent implantation step 3) mixed liquor in, jolting or vortex carry out centrifugal treating after mixing, the volume ratio of hydrophobic solvent and acetonitrile is 0.05-0.24: 1;
5) get step 4) centrifugal rear a certain amount of supernatant, upper machine carries out liquid phase or gas chromatographic analysis.
2. the method that can decompose carcinogenic aromatic amine dyestuff in Fast Measurement textile according to claim 1, is characterized in that step 3) in sample liquid long-pending with acetonitrile volume ratio be 1.2-1.9: 1.
3. the method that can decompose carcinogenic aromatic amine dyestuff in Fast Measurement textile according to claim 1, is characterized in that step 4) in the hydrophobic organic solvent volume that adds and the volume ratio of acetonitrile be 0.07-0.14: 1.
4. according to the method that can decompose carcinogenic aromatic amine dyestuff in the Fast Measurement textile described in claim 1 or 3, it is characterized in that described hydrophobic solvent is methenyl choloride or chlorobenzene or toluene or 1-hexyl-3-methylimidazole hexafluorophosphate or 1-octyl group-3-methylimidazole hexafluorophosphate.
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| CN201410217526.5A CN103983717B (en) | 2014-05-21 | 2014-05-21 | A kind of method of decomposable asymmetric choice net carcinogenic aromatic amine dyestuff in Fast Measurement textile |
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| CN201410217526.5A CN103983717B (en) | 2014-05-21 | 2014-05-21 | A kind of method of decomposable asymmetric choice net carcinogenic aromatic amine dyestuff in Fast Measurement textile |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106153780A (en) * | 2016-07-29 | 2016-11-23 | 杭州吉华江东化工有限公司 | A kind of detect the method for organochlorine residue in azo dye product |
| CN106770833A (en) * | 2017-01-10 | 2017-05-31 | 深圳市北测检测技术有限公司 | A kind of method of decomposable asymmetric choice net aromatic amine dyestuff in measure textile |
| CN110261523A (en) * | 2019-05-28 | 2019-09-20 | 广东产品质量监督检验研究院 | Testing methods of banned azo dyes and appraisement system construction method in crocodile leathercraft |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109085273B (en) * | 2018-07-10 | 2021-03-23 | 福建省产品质量检验研究院 | High performance liquid chromatography simultaneous separation detection method for 12 direct dyes in cosmetics |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671945A (en) * | 2009-09-27 | 2010-03-17 | 广东出入境检验检疫局检验检疫技术中心 | Rapid screen detection method used for banned azo dyes detection in textiles |
| CN102253138A (en) * | 2011-05-27 | 2011-11-23 | 国家皮革质量监督检验中心（浙江） | Method for detecting total amount of perfluorooctane sulphonates (PFOS) in textile and leather |
| CN102798677A (en) * | 2012-08-27 | 2012-11-28 | 江苏出入境检验检疫局工业产品检测中心 | Method for quickly screening and detecting azo dyes forbidden in textile materials, leathers and dyes using gas chromatography mass spectrometry |
-
2014
- 2014-05-21 CN CN201410217526.5A patent/CN103983717B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671945A (en) * | 2009-09-27 | 2010-03-17 | 广东出入境检验检疫局检验检疫技术中心 | Rapid screen detection method used for banned azo dyes detection in textiles |
| CN102253138A (en) * | 2011-05-27 | 2011-11-23 | 国家皮革质量监督检验中心（浙江） | Method for detecting total amount of perfluorooctane sulphonates (PFOS) in textile and leather |
| CN102798677A (en) * | 2012-08-27 | 2012-11-28 | 江苏出入境检验检疫局工业产品检测中心 | Method for quickly screening and detecting azo dyes forbidden in textile materials, leathers and dyes using gas chromatography mass spectrometry |
Non-Patent Citations (5)
| Title |
|---|
| GUOZHU LIU ET AL.: "Development of an improved method to extract pesticide residues in foods using acetontrile with magnesium sulfate and chloroform", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| 中华人民共和国国家质量监督检验检疫总局 等: "《中华人民共和国标准 GB/T 17592-2011》", 29 February 2012, 中国标准出版社 * |
| 廖思维: "食品中非法色谱测定及鸡内脏和鸡蛋中三聚氰胺分布研究", 《中国优秀硕士学位论文全文数据库 医药卫生科技辑》 * |
| 张鸣珊 等: "溶剂诱导相变萃取法用于高效液相色谱-质谱分析的血浆样品前处理", 《高等学校化学学报》 * |
| 胡小钟 等: "禁用偶氮染料检测中假阳性结果的鉴别方法", 《分析化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106153780A (en) * | 2016-07-29 | 2016-11-23 | 杭州吉华江东化工有限公司 | A kind of detect the method for organochlorine residue in azo dye product |
| CN106770833A (en) * | 2017-01-10 | 2017-05-31 | 深圳市北测检测技术有限公司 | A kind of method of decomposable asymmetric choice net aromatic amine dyestuff in measure textile |
| CN110261523A (en) * | 2019-05-28 | 2019-09-20 | 广东产品质量监督检验研究院 | Testing methods of banned azo dyes and appraisement system construction method in crocodile leathercraft |
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