CN104458966A - Detection method for forbidden azo dyes of textiles - Google Patents
Detection method for forbidden azo dyes of textiles Download PDFInfo
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- CN104458966A CN104458966A CN201410811792.0A CN201410811792A CN104458966A CN 104458966 A CN104458966 A CN 104458966A CN 201410811792 A CN201410811792 A CN 201410811792A CN 104458966 A CN104458966 A CN 104458966A
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Abstract
The invention discloses a detection method for forbidden azo dyes of textiles. The detection method comprises the following steps: accurately weighing 20 types of forbidden azo standard substances respectively, and dissolving the forbidden azo standard substances with methyl tertiary butyl ether or ethyl ether to obtain sample mixed solutions; then pipetting the sample mixed solutions with the same volume into porous particle-shaped diatomite separation columns respectively; eluting with 60mL-100mL of methyl tertiary butyl ether or ethyl ether; collecting obtained eluting solutions and concentrating the eluting solutions by using a rotary evaporator at 30-40 DEG C; and then making up the volume to be 2mL by using a corresponding eluting agent and carrying out assay determination by using a gas chromatograph-mass spectrometer. According to the detection method, methyl tertiary butyl ether and ethyl ether, which have relatively low price and strong eluting capability, are selected, so that the detection method has the advantages that the detection accuracy on forbidden carcinogenic aromatic dyes is high, injury to human bodies in a detection process is small and the detection cost is low.
Description
Technical field
The present invention relates to textile prohibitive dye detection field, specifically a kind of testing methods of banned azo dyes in textiles.
Background technology
Along with the acceleration of global industry process advances, the environmental problem that industrialization brings and on health of human body impact attract much attention gradually.The aromatic amine dyestuff used in textile product causes the great attention of security department of national governments gradually to the harm of the mankind, up to the present had 24 kinds of carcinogenic fragrant dyestuffs to be prohibited from using in textile dyeing and printing technique.Therefore, the carcinogenic aromatic amine dyestuff testing requirement that in textile, these prohibit the use also is improved gradually.At present, domestic employing GB/T 17952-2011 standard detects, but in sample pre-treatments, use ether to have a lot of defect as the eluant, eluent of liquid-solid extraction.First, the eluting power of ether is relatively weak, and can not effectively be leached out completely by the organism being adsorbed on solid silicone surface, this has a strong impact on detection sensitivity and accuracy; Secondly, ether is placed easily oxidation in atmosphere and is formed superoxide, and this oxide easily explodes in heating process, adds the danger of testing process.Ether highly volatile, easily causes Whole Body to anaesthetize, there is potential harmfulness simultaneously.In order to provide examining report more accurately, the present invention adopts that eluting power is strong, security is high, the methyl tert-butyl ether of relative low price is as eluant, eluent, realize forbidding detecting more accurately of carcinogenic aromatic amine in textile product, for consumer provides more safe and reliable supervisory detection service by selecting the flow velocity of the consumption of suitable methyl tert-butyl ether eluant, eluent and eluant, eluent.
Summary of the invention
Goal of the invention: the deficiency existed for prior art, the object of the invention is to solve now using ether as textile the carcinogenic fragrant dyestuff of forbidding detect eluant, eluent and have that accuracy is low, solvent highly volatile and the shortcoming that harmfulness is large, cost is relatively high, improve the accuracy in detection of the carcinogenic fragrant fuel of textile forbidding, provide and a kind of sensitiveer and detection method is accurately detected to textile product forbidding carcinogenic aromatic amine dyestuff.The present invention uses methyl tert-butyl ether and ether as the eluant, eluent of liquid-solid extraction respectively, contrast two kinds of eluant, eluents to 20 kinds of forbidding azo eluting powers and accuracy in detection, and the consumption of methyl tert-butyl ether and column chromatogram chromatography velocity of separation are on the impact of testing result.
Technical scheme: for realizing the object of foregoing invention, the technical solution used in the present invention is: a kind of testing methods of banned azo dyes in textiles, comprise the following steps: accurately take 20 kinds of forbidding azo standard substance methyl tert-butyl ethers respectively or ether carries out dissolving and obtains sample mix solution, then the sample mix solution of same volume is pipetted respectively in porous prilled zeyssatite separating column, and each personal 60 ~ 100mL methyl tert-butyl ether or ether carry out wash-out, collect the eluent obtained to concentrate with Rotary Evaporators under 30 ~ 40 DEG C of conditions, then analysis mensuration is carried out with being settled to 2mL with corresponding eluant, eluent for gas chromatograph-mass spectrometer (GCMS).
Wherein, above-mentioned 20 kinds of forbidding azo standard substances are 4-aminobphenyl, biphenylamine, 4-chloro-o-toluidine, 2-naphthylamines, parachloroanilinum, 2, 4-diamino anisole, 4, 4 '-diaminodiphenylmethane, 3, 3 '-dichloro-benzidine, 3, 3 '-dimethoxy benzidine, 3, 3 '-dimethylbenzidine, 3, 3 '-dimethyl-4, 4 '-diaminodiphenylmethane, 2-methoxyl-5-methylaniline, 4, 4 '-methylene-two-(2-chlorobenzene ammonia), 4, 4 '-diaminodiphenyl ether, 4, 4 '-diaminodiphenyl sulfide, adjacent benzene methanamine, 2, 4-diaminotoluene, 2, 4, 5-trimethylaniline, o-aminoanisole and 2, 4-xylidin.
Wherein, the test condition of above-mentioned gas chromatograph-mass spectrometer (GCMS): capillary chromatography column temperature is 250 DEG C; Injector temperature is 270 DEG C; Column temperature first according to rising to 60 DEG C in 1min, rise to 210 DEG C with 12 DEG C/min speed subsequently, then rise to 230 DEG C with the speed of 15min, then rise to 250 DEG C with 3 DEG C/min speed, the program that then rises to 280 DEG C with 25 DEG C/min speed heats up; Mass spectrum excuse temperature is 270 DEG C; Mass scan range is 35amu ~ 350amu; Internal standard compound is 2,4,5-trichloroaniline.
Wherein, the quality of above-mentioned 20 kinds of forbidding azo standard substances is 11.4mg ~ 12.6mg.
Wherein, above-mentioned methyl tert-butyl ether eluent 60 ~ 100mL.
Wherein, above-mentioned diethyl ether eluant 60 ~ 100mL.
Beneficial effect: the present invention is by selecting methyl tert-butyl ether and ether that relative low price, eluting power are strong as eluant, eluent, and high to the carcinogenic fragrant dyestuff accuracy in detection of forbidding, the harmfulness that testing process produces human body is little, the advantage that testing cost is low.
Embodiment
Embodiment 1:
Accurate weighing biphenylamine 11.6mg, 2,4-diaminotoluene 12.6mg, 4-chloro-o-toluidine 11.4mg, 4-aminobphenyl 11.6mg, 3,3 '-dichloro-benzidine 11.8mg, 4,4 '-methylene-two-(2-chlorobenzene ammonia) 11.0mg, 4,4 '-diaminodiphenylmethane 12.6mg is as one group; 3,3 '-dimethoxy benzidine 11.4mg, 2-methoxyl-5-methylaniline 12.6mg, parachloroanilinum 11.4mg, 4,4 '-diaminodiphenyl sulfide 12.4mg, 3,3 '-dimethylbenzidine 10.6mg, 4,4 '-diaminodiphenyl ether 11.4mg, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane 12.6mg is as one group; 2-naphthylamines 11.6mg, adjacent benzene methanamine 12.4mg, o-aminoanisole 12.2mg, 2,4-xylidin 11.8mg, 2,4-diamino anisole 11.2mg, 2,4,5-trimethylaniline 12.2mg are as one group.Above-mentioned three groups of recombined samples are dissolved with 20mL methyl tert-butyl ether, pipette 5mL and be diluted to 10mL with methyl tert-butyl ether and ether eluant, eluent respectively, then two porous prilled zeyssatite separating columns are added, and the corresponding eluant, eluent of each personal 80mL rinses, coutroi velocity 30 minutes eluents all flow out, collect eluent Rotary Evaporators to concentrate, be settled to 2mL with methyl tert-butyl ether, treat that gas chromatography-mass spectrometry analysis is tested.
Embodiment 2:
Accurate weighing biphenylamine 3.9mg, 2, 4-diaminotoluene 4.1mg, 4-chloro-o-toluidine 3.7mg, 4-aminobphenyl 4.0mg, 3, 3 '-dichloro-benzidine 3.8mg, 4, 4 '-methylene-two-(2-chlorobenzene ammonia) 4.1mg, 4, 4 '-diaminodiphenylmethane 4.2mg, 3, 3 '-dimethoxy benzidine 3.9mg, 2-methoxyl-5-methylaniline 4.3mg, parachloroanilinum 3.7mg, 4, 4 '-diaminodiphenyl sulfide 4.2mg, 3, 3 '-dimethylbenzidine 4.3mg, 4, 4 '-diaminodiphenyl ether 3.5mg, 3, 3 '-dimethyl-4, 4 '-diaminodiphenylmethane 3.8mg, 2-naphthylamines 4.0mg, adjacent benzene methanamine 3.9mg, o-aminoanisole 4.1mg, 2, 4-xylidin 4.5mg, 2, 4-diamino anisole 4.1mg, 2, 4, 5-trimethylaniline 4.3mg mixes.Dissolve above-mentioned recombined sample with 20mL methyl tert-butyl ether, pipette 5mL recombined sample solution and be diluted to 10mL with methyl tert-butyl ether and join porous prilled zeyssatite separating column and carry out wash-out with the solvent 80mL that chooses of dilution; Pipette another part of 5mL recombined sample solution simultaneously and be diluted to 10mL with ether, then joining porous prilled zeyssatite separating column and carry out wash-out coutroi velocity 30 minutes eluents with the solvent 80mL that dilution is chosen and all flow out.Collect corresponding eluent and Rotary Evaporators concentrate, be settled to 2mL with methyl tert-butyl ether, treat that gas chromatography-mass spectrometry analysis is tested.
Embodiment 3:
Two equal portions 5mL sample 10mL methyl tert-butyl ether dilutions are pipetted from the 20mL mixing forbidding azo sample the above embodiments 2, then join two porous prilled zeyssatite separating columns respectively and carry out wash-out with 60mL and 70mL solvent, coutroi velocity 30 minutes eluents all flow out, collect corresponding eluent and Rotary Evaporators concentrate, be settled to 2mL with methyl tert-butyl ether, treat that gas chromatography-mass spectrometry analysis is tested.
Embodiment 4
Two equal portions 5mL recombined sample 10mL methyl tert-butyl ether dilutions are pipetted from the 20mL mixing forbidding azo sample the above embodiments 1, then join two porous prilled zeyssatite separating columns respectively and carry out wash-out with 80mL solvent, coutroi velocity makes eluent evenly flow out in 30 minutes and 60 minutes respectively, collect corresponding eluent and Rotary Evaporators concentrate, be settled to 2mL with methyl tert-butyl ether, treat that gas chromatography-mass spectrometry analysis is tested.
According to national textile product basic fundamental safety standard GB 184014-2010, the Limited Doses≤20mg/Kg of carcinogenic aromatic amine.Above-mentioned example shows, compared to use ether as eluant, eluent, methyl tert-butyl ether is used can, by the more fully wash-out collect eluent of carcinogenic aromatic amine in test solution, to make measurement result reflect the content of forbidding azo dyes in actual sample more really as eluant, eluent.Meanwhile, for the carcinogenic aromatic amine treating fluid of different content, methyl tert-butyl ether is all better than or is equivalent to as the elute effect of eluant, eluent the detection method that current ether is used as eluant, eluent.Therefore the invention provides more accurately, testing process security more, detection method that testing cost is cheaper, realize forbidding detecting more accurately of carcinogenic aromatic amine in textile product, for consumer provides more safe and reliable supervisory detection service.
Claims (6)
1. a testing methods of banned azo dyes in textiles, it is characterized in that, comprise the following steps: accurately take 20 kinds of forbidding azo standard substance methyl tert-butyl ethers respectively or ether carries out dissolving and obtains sample mix solution, then the sample mix solution of same volume is pipetted respectively in porous prilled zeyssatite separating column, and each personal 60 ~ 100 mL methyl tert-butyl ethers or ether carry out wash-out, collect the eluent obtained to concentrate with Rotary Evaporators under 30 ~ 40 DEG C of conditions, then be settled to 2 mL with corresponding eluant, eluent and carry out analysis mensuration for gas chromatograph-mass spectrometer (GCMS).
2. a kind of testing methods of banned azo dyes in textiles according to claim 1, it is characterized in that, described 20 kinds of forbidding azo standard substances are 4-aminobphenyl, biphenylamine, 4-chloro-o-toluidine, 2-naphthylamines, parachloroanilinum, 2, 4-diamino anisole, 4, 4 '-diaminodiphenylmethane, 3, 3 '-dichloro-benzidine, 3, 3 '-dimethoxy benzidine, 3, 3 '-dimethylbenzidine, 3, 3 '-dimethyl-4, 4 '-diaminodiphenylmethane, 2-methoxyl-5-methylaniline, 4, 4 '-methylene-two-(2-chlorobenzene ammonia), 4, 4 '-diaminodiphenyl ether, 4, 4 '-diaminodiphenyl sulfide, adjacent benzene methanamine, 2, 4-diaminotoluene, 2, 4, 5-trimethylaniline, o-aminoanisole and 2, 4-xylidin.
3. a kind of testing methods of banned azo dyes in textiles according to claim 1, is characterized in that, the test condition of described gas chromatograph-mass spectrometer (GCMS): capillary chromatography column temperature is 250 DEG C; Injector temperature is 270 DEG C; Column temperature first according to rising to 60 DEG C in 1 min, rise to 210 DEG C with 12 DEG C/min speed subsequently, then rise to 230 DEG C with the speed of 15 min, then rise to 250 DEG C with 3 DEG C/min speed, the program that then rises to 280 DEG C with 25 DEG C/min speed heats up; Mass spectrum excuse temperature is 270 DEG C; Mass scan range is 35 amu ~ 350 amu; Internal standard compound is 2,4,5-trichloroaniline.
4. a kind of testing methods of banned azo dyes in textiles according to claim 1, is characterized in that, the quality of described 20 kinds of forbidding azo standard substances is 11.4 mg ~ 12.6 mg.
5. a kind of testing methods of banned azo dyes in textiles according to claim 1, is characterized in that, described methyl tert-butyl ether eluent 60 ~ 100 mL.
6. a kind of testing methods of banned azo dyes in textiles according to claim 1, is characterized in that, described diethyl ether eluant 60 ~ 100 mL.
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| CN201410811792.0A CN104458966A (en) | 2014-12-23 | 2014-12-23 | Detection method for forbidden azo dyes of textiles |
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Cited By (4)
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|---|---|---|---|---|
| CN105758963A (en) * | 2016-03-07 | 2016-07-13 | 宁波市纤维检验所 | Magnetron disperse solid extraction method for determination of residual aniline and benzidine in textiles |
| CN107860736A (en) * | 2017-10-22 | 2018-03-30 | 宁晋县质量技术监督检验所 | A kind of method for detecting forbidding azo dyes |
| CN108896669A (en) * | 2018-05-23 | 2018-11-27 | 江苏省纺织产品质量监督检验研究院 | Textile azo rapid detection method |
| CN115201382A (en) * | 2022-09-08 | 2022-10-18 | 沧州大化股份有限公司 | Method for detecting sample containing diaminotoluene |
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| CN103033579A (en) * | 2012-12-27 | 2013-04-10 | 通标标准技术服务(上海)有限公司 | Rapid determination method for content of banned azo dye |
| US8519176B1 (en) * | 2009-10-05 | 2013-08-27 | Boehringer Ingelheim International Gmbh | Process for preparation of substituted P-aminophenol |
| CN104155380A (en) * | 2014-08-15 | 2014-11-19 | 广州衡创测试技术服务有限公司 | Detection method for banned azo-dye in textile |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8519176B1 (en) * | 2009-10-05 | 2013-08-27 | Boehringer Ingelheim International Gmbh | Process for preparation of substituted P-aminophenol |
| 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 |
| CN103033579A (en) * | 2012-12-27 | 2013-04-10 | 通标标准技术服务(上海)有限公司 | Rapid determination method for content of banned azo dye |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105758963A (en) * | 2016-03-07 | 2016-07-13 | 宁波市纤维检验所 | Magnetron disperse solid extraction method for determination of residual aniline and benzidine in textiles |
| CN107860736A (en) * | 2017-10-22 | 2018-03-30 | 宁晋县质量技术监督检验所 | A kind of method for detecting forbidding azo dyes |
| CN108896669A (en) * | 2018-05-23 | 2018-11-27 | 江苏省纺织产品质量监督检验研究院 | Textile azo rapid detection method |
| CN115201382A (en) * | 2022-09-08 | 2022-10-18 | 沧州大化股份有限公司 | Method for detecting sample containing diaminotoluene |
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