CN104697835B - Aromatic amine detection mixed mark solution of standard and preparation method thereof and purposes in textile - Google Patents
Aromatic amine detection mixed mark solution of standard and preparation method thereof and purposes in textile Download PDFInfo
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- CN104697835B CN104697835B CN201510131815.8A CN201510131815A CN104697835B CN 104697835 B CN104697835 B CN 104697835B CN 201510131815 A CN201510131815 A CN 201510131815A CN 104697835 B CN104697835 B CN 104697835B
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- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 82
- 238000001514 detection method Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000004753 textile Substances 0.000 title claims abstract description 32
- 238000010561 standard procedure Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 31
- KLLLJCACIRKBDT-UHFFFAOYSA-N 2-phenyl-1H-indole Chemical compound N1C2=CC=CC=C2C=C1C1=CC=CC=C1 KLLLJCACIRKBDT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003381 stabilizer Substances 0.000 claims abstract description 26
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 24
- -1 aromatic amine compounds Chemical class 0.000 claims description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 15
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 8
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 8
- 229940085675 polyethylene glycol 800 Drugs 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 230000001186 cumulative effect Effects 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 229960003511 macrogol Drugs 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000007689 inspection Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 175
- 239000000523 sample Substances 0.000 description 39
- 238000012360 testing method Methods 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 20
- 239000000975 dye Substances 0.000 description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 239000000987 azo dye Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 235000019504 cigarettes Nutrition 0.000 description 7
- 239000000284 extract Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000008676 import Effects 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 238000010200 validation analysis Methods 0.000 description 5
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical class COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 description 4
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007979 citrate buffer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000013074 reference sample Substances 0.000 description 4
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical class CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 3
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 230000000711 cancerogenic effect Effects 0.000 description 3
- 231100000315 carcinogenic Toxicity 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 229940079826 hydrogen sulfite Drugs 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000012224 working solution Substances 0.000 description 3
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical class NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 2
- DSBIJCMXAIKKKI-UHFFFAOYSA-N 5-nitro-o-toluidine Chemical class CC1=CC=C([N+]([O-])=O)C=C1N DSBIJCMXAIKKKI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 101100321447 Arabidopsis thaliana ZHD4 gene Proteins 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- KUWAAZMPJBFLEO-UHFFFAOYSA-N n,n,2-trichloroaniline Chemical compound ClN(Cl)C1=CC=CC=C1Cl KUWAAZMPJBFLEO-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
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- 239000011885 synergistic combination Substances 0.000 description 2
- 238000004885 tandem mass spectrometry Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 150000004999 2,4-diaminotoluenes Chemical class 0.000 description 1
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical class CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 1
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical class CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 1
- PFRYFZZSECNQOL-UHFFFAOYSA-N 2-methyl-4-[(2-methylphenyl)diazenyl]aniline Chemical compound C1=C(N)C(C)=CC(N=NC=2C(=CC=CC=2)C)=C1 PFRYFZZSECNQOL-UHFFFAOYSA-N 0.000 description 1
- CXNVOWPRHWWCQR-UHFFFAOYSA-N 4-Chloro-ortho-toluidine Chemical class CC1=CC(Cl)=CC=C1N CXNVOWPRHWWCQR-UHFFFAOYSA-N 0.000 description 1
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical class NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 description 1
- 101100321442 Arabidopsis thaliana ZHD1 gene Proteins 0.000 description 1
- 101100377293 Arabidopsis thaliana ZHD10 gene Proteins 0.000 description 1
- 101100377295 Arabidopsis thaliana ZHD11 gene Proteins 0.000 description 1
- 101100377298 Arabidopsis thaliana ZHD12 gene Proteins 0.000 description 1
- 101100377299 Arabidopsis thaliana ZHD13 gene Proteins 0.000 description 1
- 101100377300 Arabidopsis thaliana ZHD14 gene Proteins 0.000 description 1
- 101100321445 Arabidopsis thaliana ZHD3 gene Proteins 0.000 description 1
- 101100321449 Arabidopsis thaliana ZHD5 gene Proteins 0.000 description 1
- 101100321455 Arabidopsis thaliana ZHD7 gene Proteins 0.000 description 1
- 101100321457 Arabidopsis thaliana ZHD8 gene Proteins 0.000 description 1
- 101100321459 Arabidopsis thaliana ZHD9 gene Proteins 0.000 description 1
- 102100035793 CD83 antigen Human genes 0.000 description 1
- 102100023033 Cyclic AMP-dependent transcription factor ATF-2 Human genes 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 102100027490 H2.0-like homeobox protein Human genes 0.000 description 1
- 101000946856 Homo sapiens CD83 antigen Proteins 0.000 description 1
- 101000974934 Homo sapiens Cyclic AMP-dependent transcription factor ATF-2 Proteins 0.000 description 1
- 101001081101 Homo sapiens H2.0-like homeobox protein Proteins 0.000 description 1
- DSNPTNDJYAUVQR-UHFFFAOYSA-N NC1=CC=CC=C1.CC1=CC=C(C(=C1)C)C Chemical compound NC1=CC=CC=C1.CC1=CC=C(C(=C1)C)C DSNPTNDJYAUVQR-UHFFFAOYSA-N 0.000 description 1
- 229910006147 SO3NH2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 239000005703 Trimethylamine hydrochloride Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000004853 microextraction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 238000000611 regression analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The present invention relates to aromatic amine detection in a kind of textile mixed mark solution of standard and preparation method thereof and purposes, the preparation method comprises the following steps：S1：Prepare 23 kinds of singly mark solutions of aromatic amine；S2：Prepare stabilizer I solution and stabilizer II solution；S3：Prepare the mixed mark solution of the standard.In the method, by the use of specific addition sequence and stabilizer, so as to obtain detecting the mixed mark solution of standard of excellent performance.The method is widely used on textile inspection field and the mixed mark solution industrialization of detection standard with resulting mixed mark solution and is worth and market prospects.
Description
Technical field
Standard sample and preparation method thereof the present invention relates to be used to detect harmful chemical, relates more specifically to weaving
Aromatic amine detection mixed mark solution of standard and preparation method thereof, belongs to detection and the analytical technology of harmful substance in textile in product
Field.
Background technology
China is one of DYE PRODUCTION country maximum in the world, is also textile exports big country.But in face of external such as U.S.
The blue laws such as state, European Union and the Green Trade Barrier that builds, and the environmental consciousness with textile clothing enterprise enhancing,
Production green, the textile garment of environmental protection turn into the most important thing of enterprise.
Currently, major part is required for by diazotising and coupling reaction etc. the dyestuff on domestic and international market in process of production
The reaction mechanism mechanism of reaction.Azo is the basic substance of formation color in dyestuff, if having abandoned azo structure, then most dyestuff
Base color will be unable to generation.Therefore, azo structure has special consequence in dyestuff, but has a small number of azo structures
Dyestuff can resolve into various aromatic amine compounds that can be carcinogenic under certain electrochemical conditions, and these compounds are exactly by European Union
The chemical substance forbidden.
Compared with external increasingly strict standard, dyestuff of the country containing such material still accounts for 5% or so of whole dyestuffs,
About 104 kinds prohibitive dyes are also more or less being used.Therefore, this underproof product of detection is still largely deposited in recent years
, this health to the people, especially children cause certain potential threat, cause society extensive concern.
Just because of the potential carcinogenic harm of aromatic amine, researcher is for the aromatic amine detection side in many kinds of substance
Method has carried out substantial amounts of research, and achieves many achievements, for example：
CN102213696A discloses a kind of assay method of aromatic amine in plasticine, and the method comprises the following steps：Will
Plasticine is cut into small pieces, and using methyl alcohol, ethanol, isopropanol or acetonitrile to plasticine fritter ultrasonic extraction, obtains extract solution；Removal
Organic solvent addition hydrogensulfite solution in the extract solution carries out reduction reaction at 60-80 DEG C；Will be anti-after reaction
Liquid is answered to adjust pH 10-12, then through SPE column purification, wash-out obtains eluent, and eluent enters gas chromatography-mass spectrum
Instrument determines aromatic amine, so as to determine its content.
CN102060712A discloses a kind of aromatic amine haptens for detecting azo dyes, the aromatic amine haptens
Can be recognized by immunocompetent cell after being connected with carrier, and produce the antibody with expected selectivity and compatibility, so as to build
The enzyme-linked immune analytic method of the aromatic amine small molecule of vertical azo dyes, is easy to accurate to such material, efficient and inspection in time
Survey.
CN102323342A discloses a kind of detection method to aromatic amine compound in sample, and affiliated detection method includes
Two processes of extraction and detection, with ionic liquid [C6MIN][PF6] or [C4MIM][PF6] extractant is made, it is auxiliary using eddy oscillating
Ionic liquid micro-extraction is helped, is detected using supper-fast liquid chromatograph, testing result is obtained using Regression Equations.Institute
State that detection method sensitivity is high, detection limit is low, and precision is good；Extractant is made using green reagent, it is to avoid the making of organic reagent
With reducing environmental pollution；With it is quick, stabilization the features such as, substantially reduce the time of sample detection；Can apply to detection each
The aromatic amine compound in water sample is planted, there is certain social effect for the health of environmental protection and the mankind.
CN102279237A is related to a kind of method of detecting aromatic amine in cigarette mainstream smoke by using gas chromatography-tandem mass spectrometry,
Methods described is, using the aromatic amine compounds in cambridge filter trapping cigarette mainstream smoke condensate, to be extracted with hydrochloric acid solution
Afterwards, after through dichloromethane washing, NaOH reduction, n-hexane extraction, spread out using PFPA and trimethylamine hydrochloride
Biochemistry, after concentration, is detected using gas chromatography tandem mass spectrometry combined instrument, main fragrance in measure cigarette mainstream flue gas
The content of aminated compounds.The analysis determining method compared with the analysis method of aromatic amine in original cigarette mainstream flue gas,
Sample pre-treatments are simplified, sensitivity is higher, the repeatability and the rate of recovery of experiment are fine, it is adaptable to the analysis of batch samples.
CN102507561A discloses forbidding azo dyes quick detection kit in a kind of dyed textiles, including：1)
Extracts reagent A：Methyl tertiary butyl ether, 10ml；2) extracts reagent B：0.1-1.0mol/L hydrochloric acid solutions, 5ml；3) reagent 1：50g/L
NaNO2Solution, 0.05ml；4) reagent 2：25g/L NH4SO3NH2Solution, 0.5ml；5) reagent 3：Concentration expressed in percentage by volume is 2%
O-methoxyphenol ethanol water, 1ml；6) reagent 4：0.5mol/L NaOH solutions, 1ml；7) go back original reagent 1：0.06mol/
L, pH=6.0 citrate buffer, 16ml；8) go back original reagent 2：200mg/ml hydrogensulfite solutions, 3.0ml.It is adopted
Pre-treatment is carried out with liquid-liquid extraction textile reducing solution and the method decolourized, by chromogenic assay aromatic amine, pre-treatment is simple, fast
Victory, enormously simplify original step, without any instrument and equipment in measure, realize the fast of textile forbidding azo dyes detection
Fast examination detection.
CN102798677A discloses one kind gas chromatography-mass spectrum to disabling azo dye in textile, leather and dyestuff
The rapid screening detection method of material, the described method comprises the following steps：1) sample preparation：General textile, terylene are knitted respectively
Thing, leather and dyestuff carry out sample preparation, take sample and are placed in salable reactor, add citrate buffer solution and by instead
Answer device to be placed in 70 ± 2 DEG C of water-baths to be kept for 10 minutes；2) reduction reaction：To being added in described reactor, sodium dithionite is molten
After liquid, and closed shaking, reactor is placed in again in 70 ± 2 DEG C of water-baths and is kept for 15 minutes, be subsequently placed in cold in frozen water mixed liquor
But 1-3 minutes；3) extract：Concentration is added to be worked for the 245 trichloroaniline internal standard of 2mg/L to accurate in described reactor
Liquid, reactor is closed, after shaking and standing, anhydrous sodium sulfate is added, enter as sample after supernatant liquor after two phase stratification, is taken
Row gas chromatography-mass spectrometry analysis；4) gas chromatography-mass spectrometry analysis：Sample injection gas phase color prepared by standard specimen and step 3 is taken respectively
Spectrum-mass spectrograph, by regulation condition test and analyze, the solute of the standard specimen in 24 kinds of disabling aromatic amines except adjacent amino azo
21 kinds of disabling aromatic amine standard substances, aniline and 2,4,5- trichlorines outside toluene, 5- nitro-o-toluidines and 4- aminoazabenzols
Aniline, the concentration of each solute is 2mg/L；5) screening judges：Responded by the signal of the trichloroaniline of internal standard compound 2,4,5-, analysis
Whether extraction process and instrument state are normal；Determined by the mass spectrogram of the retention time and each component of comparative sample and standard specimen
Property analysis, internal standard method carries out quantitative analysis；If the retention time or mass spectrum of aromatic amine are inconsistent with standard in sample, or test
Value is less than 5mg/kg, can directly be judged as negative sample；If the retention time and mass spectrum of aromatic amine are consistent with standard in sample,
And test value be more than 5mg/kg when, be judged to suspect positive.
CN103760288A discloses a kind of assay method of forbidding azo dyes in Cigarette paper, and methods described includes：
Reducing solution is added after Cigarette paper sample is shredded, makes azo material in citric acid solution by hydrosulfurous acid sodium reduction
Into aromatic amine, then extract the aromatic amine in solution with the method for liquid-liquid extraction, it is concentrated after redissolved with methyl alcohol, use liquid chromatogram
Tandem mass spectrum combined instrument is measured, and inner mark method ration is comprised the following steps that：A, Cigarette paper sample is carried out to be cut；
The extraction of b, sample：Sample is cut into the fragment of 5mm × 5mm or so, is well mixed；Weigh 0.5g samples；Fragment is placed in
In 50ml conical flask with stopper, the citrate buffer solution for adding 15ml to be preheated to 70 ± 2 DEG C, fierce shake makes liquid immersion sample,
Placed 330 minutes in 70 ± 2 DEG C of water-baths；Hydrosulfurous acid sodium water solution 3ml is added, is kept for 70 ± 2 DEG C, reacted 30 minutes；
Then in being cooled to room temperature in 2 minutes in the cold water for conical flask being flowed；C, sample purification：1ml is separately added into toward triangular flask
20% sodium hydroxide solution, the anhydrous sulphur of 100 μ l internal standards (D9-4- amino connection is stupid) solution, 10ml t-butyl methyl ethers and 8-10g
Sour sodium, vibrates 10 minutes, then stands 5 minutes, takes the supernatant of 1ml, adds the acetum of 2-3 drops, nitrogen to be blown to do to the greatest extent,
Redissolved with the methyl alcohol of 1ml, enter LC-MS/MS analyses；D, preparation standard working solution：The various aromatic amine standards of 0.01g are weighed respectively
Product are configured to methanol dilution and finally the standard working solution with concentration gradient in 10ml volumetric flasks；E, liquid chromatogram-
Tandem mass spectrum is determined：The standard working solution of the various concentrations that absorption is prepared, injects liquid chromatography-tandem mass spectrometry instrument；F, virtue
The calculating of fragrant amine measurement result carries out the quantitative analysis of residual quantity with internal standard method, i.e., with each aromatic amine and interior target quota ion pair
Peak area carries out regression analysis to its respective concentration, obtains standard curve, and coefficient correlation is more than or equal to 0.999, after extraction
Sample is measured, and measures detection aromatic amine and interior target quota ion pair peak area ratio, standard curve is substituted into, in trying to achieve sample
Aromatic amine residual quantity.
The method that CN103983717A discloses decomposable asymmetric choice net carcinogenic aromatic amine dyestuff in a kind of quick measure textile includes
Following steps：1) it is put into after textile sample to be checked is shredded in tool plug reactor, is subsequently added into warmed-up Citrate buffer
Liquid, is placed in water-bath after shaking mixing and is incubated；2) closed shaking mixing after hydrogensulfite solution is added, then tool is filled in into reaction
Device is incubated in water-bath；Then it was cooled to room temperature in 2 minutes；3) a certain amount of sample liquid is pipetted from container in tool plug centrifuge tube
In, while adding a certain amount of acetonitrile to be well mixed；4) pipette a certain amount of hydrophobic solvent implantation step 3) mixed liquor in,
Centrifugal treating is carried out after shaking or vortex mixing；5) step 4 is taken) a certain amount of supernatant after centrifugation, upper machine carries out liquid phase or gas
Analysis of hplc.
CN104165952A discloses a kind of detection method of forbidding azo dyes in ink, coating, paint, it include with
Lower step：(1) extraction of disperse dyes：(1.1) by ink, paint drying and pulverize, it is standby as sample；(1.2) weigh
1.0g samples add 25ml methyl alcohol in 50ml screw sockets test tube with cover in test tube, tighten test tube cap, are placed in 40 DEG C of water-baths and surpass
In sound wave, ultrasonic extraction 60 minutes；(1.3) take out test tube and be cooled to room temperature, extract solution is filtered into 150ml round-bottomed flasks,
Then 5ml methyl alcohol drip washing test tubes are used, leacheate is with spline filter to round-bottomed flask；(1.4) filtrate is under the conditions of 50 DEG C of 300mbar
Rotated near dry with Rotary Evaporators, will be evaporated thing with 2 × 1ml methyl alcohol and be transferred in clean tube；(2) reductive cleavage：(2.1)
Add 15ml to be preheated to the sodium citrate buffer of (70 ± 2) DEG C in test tube, cover tightly test tube cap and be placed in (70 ± 2) test tube
(30 ± 1) minute is incubated in DEG C water-bath；(2.2) test tube cap is opened, 3.0ml reducing agents are added, test tube cap is tightened and is firmly shaken
Shake, be subsequently placed in insulation (30 ± 1) minute in (70 ± 2) DEG C water-bath；(2.3) test tube is taken out to cool down test tube in 2 minutes
To room temperature；(3) separation of amine：(3.1) sodium hydroxide solution of 0.2ml 10% is added in test tube, test tube cap is tightened and is exerted oneself
Shake；5ml t-butyl methyl ethers are added in test tube again, test tube cap is tightened, is placed on shaking table and is shaked under 250 revs/min 30 minutes；
(3.2) test tube is removed, adds anhydrous sodium sulfate, stratification to take upper organic phase in test tube, excessively organic miillpore filter is extremely
In 2ml gas chromatographic sample introductions bottle, GC headspace analysis are supplied.
CN104230737A is disclosed and a kind of be can be used for the organic cooperation of transition metal of selective enumeration method arylamine pollutant
The preparation method of thing, the transition that transition metal zinc salt and 5- amino isophthalic acids (L) part are formed is prepared using solvent-thermal method
Metal organic complex, its specific preparation process is：L parts, Zn (NO3)2·6H2O in molar ratio 1:1 mixing is placed in polytetrafluoro
In ethene inner bag, then isothermal reaction 120 hours at 85 DEG C naturally cool to room temperature, and filtering, products therefrom is washed with DMF,
Drying at room temperature, obtains bulk crystals C16H14N2O10Zn2。
As described above, various methods for detecting fragrant amine content are had been disclosed in the prior art, in these methods
In, it is necessary to press standard sample solution using to fragrance, but current present situation is opened in mandatory national standards GB 18401-2010
After beginning to implement, the sample size of domestic testing agency's inspection decomposable asymmetric choice net aromatic amine dyestuff is significantly increased, and national testing agency is annual
The about batch of detection decomposable asymmetric choice net aromatic amine dyestuff project about 500,000 altogether, undertakes that the item detection mechanism is numerous, and detection method is related to
To GB, DIN, EU criteria etc..
But, in the Project Process is detected, the aromatic amine compound standard sample for using really comes from for testing agency
The reference sample that external chromatogram running stores company provides.The standard sample that the country is used is base of the different manufacturers in import sample
Voluntarily prepared on plinth, it is different so as to result in concentration, purity etc., occur in that actually detected concentration is inconsistent with nominal concentration and show
As causing the assay of surveying under the reference sample using different chromatogram running stores companies there is no comparativity, even to same
One submitted sample, the detection data between different testing agencies also differs greatly.For example, organized in the whole nation in 2008 once may be used
Decompose aromatic amine compound contrasting between laboralories, have 20 laboratories in 59 laboratories of participation because the reference sample that uses not
Unanimously, so as to the testing result for causing the different experiments room of same sample has significant deviation.
The present inventor in order to verify the reason for such deviation is present, and by the decomposable asymmetric choice net aromatic amine hybrid reference sample of import
(hereinafter referred to as import is mixed marks, and contained aromatic amine concentration is 50ppm) carries out concentration checking with GC/MS.Specific authentication
Method is：The decomposable asymmetric choice net aromatic amine solid list mark day of the famous foreign producer (such as Germany Dr.Ehrenstorfer) that will be bought
Flat (μ g of sensibility reciprocal 1) is weighed, and is configured to the standard singly mark solution (i.e. concentration is 50ppm) of concentration 50mg/L, using 21 kinds of standards
The method that singly mark solution replaces sample introduction with the mixed mark solution (concentration of wherein every kind of aromatic amine is 50ppm) of import, according to country
Standard criterion method of testing GB/T 17592-2011 are measured, so as to demonstrate to 21 kinds of concentration of standard singly mark solution, knot
Fruit see the table below 1.
Table 1：The mixed mark of import and single mark concentration difference list
Note：" * " represents wherein two kinds of characteristic ions of material (amu) of serial number 20,21, single mark (ppm) and mixed mark
(ppm) 121,50 and 66.8 are respectively.
As can be seen from the above table, when molten to standard list mark using the mixed mark solution of the standard comprising various violated aromatic amine compounds
When liquid is verified, there is larger even very big difference between resulting checking concentration and actual concentrations, also exactly
Due to the difference, appearance and generation that above-mentioned even same sample but has the phenomenon of dramatically different testing result are result in.
Therefore, based on drawbacks described above, in actual detection process, preparation deviation is smaller, more accurately meet detection
It is to be badly in need of that required standard mixes mark solution, and it has good industrial applications potentiality and real value, this also exactly this hair
Leaned on basis where the bright power being accomplished.
The content of the invention
In China, according to mandatory national textile product specification GB 18401-2010《National textile product basic security skill
Art specification》With detection method GB/T 17592-2011 in specification《Testing methods of banned azo dyes in textiles》Requirement, disabling
The detection species of dyestuff has 24 kinds, is specifically shown in table 2 below：
Table 2：Disabling aromatic amine compound
Wherein o-aminoazotoluene, 5- nitro-o-toluidines are separately disassembled into after being processed specified in detection method
Ortho-aminotoluene and 2,4- diaminotoluene, and 2,4- dimethylanilines and 2,6- dimethylanilines are isomer, in gas phase
The operating method specified using above-mentioned examination criteria in chromatogram cannot be distinguished effectively, and 4- aminoazabenzols are according to GB/T
When 17592-2011 is detected, aniline and Isosorbide-5-Nitrae-phenylenediamine can be decomposed into.Therefore the 24 kinds of taboos for being detected the need for defined in a standard
On the basis of with aromatic amine, it is only necessary to GB 18401-2010 and GB/T are met by the hybrid standard material for preparing 23 kinds
Detection requirement (see the table below 3) of 17592-2011.
Table 3：Prepare material needed for the standard liquid of detection disabling aromatic amine compound
Based on the principle, in order to solve the mixed mark solution of external import as indicated above with standard singly mark solution in concentration
Significant difference, the present inventor has carried out substantial amounts of further investigation to this, after creative work has been paid, so as to complete this
Invention.
Specifically, the present invention relates to aromatic amine detection standard sample and preparation method thereof in a kind of textile.It is more special
It is other, the present invention relates to following aspects.
One side, the present invention relates to the preparation method that aromatic amine detection standard in a kind of textile mixes mark solution,
Methods described comprises the following steps：
S1：Prepare 23 kinds of singly mark solutions of aromatic amine；
S2：Prepare stabilizer I solution and stabilizer II solution；
S3：Prepare the mixed mark solution of the standard.
In the preparation method of the invention, the step S1 is specially：23 kinds of aromatic amine compounds are weighed respectively, it is molten
Solution carries out constant volume in ultra-pure water, obtains the singly mark solution of every kind of aromatic amine.
Wherein, in step S1,23 kinds of aromatic amines are following aromatic amine compound：
Wherein, in step S1, weighed using electronic balance, for example, the high precision electro that sensibility reciprocal is 1 μ g can be used
Sub- balance is weighed, and can so ensure that precision reaches hundred a ten thousandths.The electronic balance of such sensibility reciprocal is very known
Product, can be obtained by commercially available channel, this is no longer going to repeat them.
Wherein, in step S1, resistivity of the ultra-pure water at 25 DEG C is at least 18M Ω cm, for example, can make
It is prepared with Millipore Corp. Mili-Q type one-level water preparation apparatus.
Wherein, in step S1,23 kinds of aromatic amines of respective quality are weighed by using above-mentioned high Accuracy Electronic Balance,
And be dissolved into above-mentioned ultra-pure water, then carry out constant volume, for example can constant volume to 5-20ml, for example can for 5ml, 10ml,
15ml or 20ml.Certainly also dependent on be actually needed and constant volume to other volumes, such as higher than 20ml.
Wherein, in step S1, the concentration of the singly mark solution can be for example 500-4000ppm, for example, can be
500ppm, 1000ppm, 1500ppm, 2000ppm, 2500ppm, 3000ppm, 3500ppm or 4000ppm.It is of course also possible to root
Other concentration are configured to according to being actually needed.
Wherein, in step S1, the concentration of the singly mark solution of 23 kinds of aromatic amines may be the same or different, but in order to count
The convenient consideration that the convenience counted in is operated with subsequent step, preferably the concentration all same of this 23 kinds of singly mark solutions of aromatic amine.
In the preparation method of the invention, the step S2 is specially：Stabilizer I and stabilizer II is weighed respectively,
Be dissolved in above-mentioned ultra-pure water, so as to obtain stabilizer I solution that mass percent concentration is in the range of 0.5-1.5% and
Stabilizer II solution.
Wherein, in step S2, the stabilizer I is polyethylene glycol (PEG), such as polyethylene glycol 200 (PEG-
200), PEG400 (PEG-400), Macrogol 600 (PEG-600) or polyethylene glycol-800 (PEG-800), most preferably
Polyethylene glycol 200 (PEG-200).
Wherein, in step S2, the stabilizer II is tetraethylene glycol (TEG).
Wherein, in step S2, the mass percent concentration of the stabilizer I solution and stabilizer II solution is
0.5-1.5%, for example, can be 0.5%, 1% or 1.5%.For the convenience on operating and measuring, preferably both concentration is identical.
In the preparation method of the invention, the step S3 is specially：Respectively in removing step S1 each is singly marked
Stabilizer I solution and stabilizer II solution in solution, step S2, and mixing, Ran Houyong are added in particular order
Acetonitrile constant volume, so as to obtain the mixed mark solution of the standard.
Wherein, in step S3, the volume of each singly mark solution can mix the concentration of mark solution according to final gained standard
Calculated with volume and obtained, this is belonged to Conventional wisdom in this area and means and (for example pipettes that volume=(the mixed mark of standard is molten
Concentration × the volume of liquid)/high concentration singly mark solution concentration), this is no longer going to repeat them.
Wherein, in step S3, pipette stabilizer I solution volume and pipetted stabilizer II solution volume with
The ratio of the cumulative volume of all pipetted singly mark solutions is 1:500-1500 (volume of i.e. pipetted stabilizer I solution with it is all
The ratio of the cumulative volume of pipetted singly mark solution, and pipetted stabilizer II solution volume and all pipetted singly mark solutions
The ratio of cumulative volume is 1:500-1500, unless otherwise defined, following identical description is respectively provided with so identical containing
Justice), for example can be 1:500、1:1000 or 1:1500.
Wherein, in step S3, the specific order (adding order by merging) is as follows：
In upper table, A-Y represents sequentially order of addition, i.e., then the 4- aminobphenyls that addition A is referred at first add B and refer to
The benzidine in generation, then the 4- chloro-o-toluidines ... of C references are added until the stabilizer II that refer to of addition Y, so as to complete to own
The addition of material.The inventors discovered that, order of addition is mixed accuracy of the mark solution in detection process and is covered for ultimate criterion
Lid rate aspect have it is conclusive significantly affect, be specifically shown in subsequent embodiment.
Wherein, in step S3, the acetonitrile can be trifluoroacetic acid aqueous solution, can so ensure that standard mixes the pure of mark solution
Degree.
Wherein, in step S3, in order to be conducive to the contrast of the result for detecting sample, preferably gained standard is mixed marks solution
In 23 kinds of respective concentration all sames of aromatic amine, for example can be 20-100ppm, further for example can for 20ppm, 30ppm,
40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm or 100ppm.Certainly it is other concentration also dependent on being actually needed,
For example it is higher than 100ppm.
Second aspect, is mixed the present invention relates to aromatic amine detection standard in the textile that is prepared by the above method
Mark solution.
3rd aspect, the mixed mark solution of aromatic amine detection standard the present invention relates to be obtained by above-mentioned preparation method is existed
Purposes in the violated aromatic amine detection of textile
The inventors discovered that, when the mixed mark solution of aromatic amine detection standard in the textile prepared using methods described
With good detection stability and Full coverage (all of violated aromatic amine can be detected), so as to may be used on textile
In field in the detection of violated aromatic amine, with high sensitivity.
It is as described above, the invention provides a kind of mixed mark solution and its preparation side of standard of aromatic amine detection in textile
Method, in the preparation method, by the factor such as the selection and use of specified stabiliser, the specific order of addition of all kinds of aromatic amines
Synergistic combination/effect, so as to obtained with excellent sensitivity and detection coverage rate mixed mark solution, can be used for textile neck
In the detection of the violated aromatic amine in domain, with good industrial applications potentiality and application prospect.
Specific embodiment
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, not constitutes any type of any restriction to real protection scope of the invention, more non-to incite somebody to action
Protection scope of the present invention is confined to this.
Embodiment 1：Standard mixes the preparation of mark solution
S1：Prepare 23 kinds of singly mark solutions of aromatic amine
Weigh 23 kinds of aromatic amine compounds in following table respectively using the high Accuracy Electronic Balance that sensibility reciprocal is 1 μ g, be dissolved into
Resistivity at 25 DEG C is at least in the ultra-pure water of 18M Ω cm, and constant volume obtains the concentration of every kind of aromatic amine to 10ml
It is the singly mark solution of 2000ppm；
23 kinds of aromatic amines are following aromatic amine compound：
S2：Prepare stabilizer I solution and stabilizer II solution
Claim polyethylene glycol 200 (being abbreviated as PEG-200 below) and tetraethylene glycol respectively, be dissolved in used in step S1
Ultra-pure water in, so as to obtain PEG-200 solution and tetraethylene glycol solution that mass percent concentration is 1%.
S3：The mixed mark solution of preparation standard
Each singly mark solution, PEG-200 solution and tetraethylene glycol solution in step S2 in difference removing step S1, and press
Mixing is added according to the order in following table, trifluoroacetic acid aqueous solution constant volume is then used, it is equal so as to obtain wherein every kind of aromatic amine concentration
For the standard of 50ppm mixes mark solution, HB1 is named as；
Wherein, the volume and all pipetted singly mark solutions of PEG-200 solution and pipetted tetraethylene glycol solution are pipetted
The ratio of cumulative volume is 1:500.
Wherein, in step S3, the specific order (adding order by merging) is as follows：
Embodiment 2：Standard mixes the preparation of mark solution
S1：Prepare 23 kinds of singly mark solutions of aromatic amine
In addition to quality difference is weighed so as to obtain the singly mark solution that the concentration of every kind of aromatic amine is 1000ppm, other are equal
The step of with embodiment 1, S1 was identical；
S2：Prepare stabilizer I solution and stabilizer II solution
Except weighed PEG-200 is different with the quality of tetraethylene glycol 1.5% is so as to obtain mass percent concentration
Outside PEG-200 solution and tetraethylene glycol solution, S2 is identical the step of other are with embodiment 1.
S3：The mixed mark solution of preparation standard
Except changing the volume of each singly mark solution that is pipetted and pipetted PEG-200 solution and to pipette tetraethylene glycol molten
The volume of liquid is 1 with the ratio of the cumulative volume of all pipetted singly mark solutions:1000, so as to obtain wherein every kind of aromatic amine concentration
It is the step of standard of 100ppm is mixed to be marked outside solution, and other are with embodiment 1 S3 identical；By resulting wherein every kind of fragrance
The mixed mark solution of standard that amine concentration is 100ppm is named as HB2.
Embodiment 3：Standard mixes the preparation of mark solution
S1：Prepare 23 kinds of singly mark solutions of aromatic amine
In addition to quality difference is weighed so as to obtain the singly mark solution that the concentration of every kind of aromatic amine is 3000ppm, other are equal
The step of with embodiment 1, S1 was identical；
S2：Prepare stabilizer I solution and stabilizer II solution
Except weighed PEG-200 is different with the quality of tetraethylene glycol 0.5% is so as to obtain mass percent concentration
Outside PEG-200 solution and tetraethylene glycol solution, S2 is identical the step of other are with embodiment 1.
S3：The mixed mark solution of preparation standard
Except changing the volume of each singly mark solution that is pipetted and pipetted PEG-200 solution and to pipette tetraethylene glycol molten
The volume of liquid is 1 with the ratio of the cumulative volume of all pipetted singly mark solutions:1500, so as to obtain wherein every kind of aromatic amine concentration
It is the step of standard of 20ppm is mixed to be marked outside solution, and other are with embodiment 1 S3 identical；By resulting wherein every kind of fragrance
The mixed mark solution of standard that amine concentration is 20ppm is named as HB3.
Embodiment 4：Standard mixes the preparation of mark solution
S1：Prepare 23 kinds of singly mark solutions of aromatic amine
In addition to quality difference is weighed so as to obtain the singly mark solution that the concentration of every kind of aromatic amine is 4000ppm, other are equal
The step of with embodiment 1, S1 was identical；
S2：Prepare stabilizer I solution and stabilizer II solution
S2 is identical for the step of step is with embodiment 1.
S3：The mixed mark solution of preparation standard
Except change pipette each singly mark solution volume, be 70ppm so as to obtain wherein every kind of aromatic amine concentration
The mixed mark solution of standard outside, S3 is identical the step of other are with embodiment 1；Resulting wherein every kind of aromatic amine concentration is
The mixed mark solution of the standard of 70ppm is named as HB4.
Embodiment 5-28：Standard mixes the preparation of mark solution
In addition to following order of addition difference, other are identical with correspondence embodiment, so as to obtain different mixed mark solution：
Embodiment 5：Order of addition is BACDEFGHIJKLMNOPQRSTUVWXY, correspondence embodiment 1, the mixed mark solution of gained
It is named as HB5.
Embodiment 6：Order of addition is ACBDEFGHIJKLMNOPQRSTUVWXY, correspondence embodiment 2, the mixed mark solution of gained
It is named as HB6.
Embodiment 7：Order of addition is ABDCEFGHIJKLMNOPQRSTUVWXY, correspondence embodiment 3, the mixed mark solution of gained
It is named as HB7.
Embodiment 8：Order of addition is ABCEDFGHIJKLMNOPQRSTUVWXY, correspondence embodiment 4, the mixed mark solution of gained
It is named as HB8.
Embodiment 9：Order of addition is ABCDFEGHIJKLMNOPQRSTUVWXY, correspondence embodiment 1, the mixed mark solution of gained
It is named as HB9.
Embodiment 10：Order of addition is ABCDEGFHIJKLMNOPQRSTUVWXY, correspondence embodiment 2, the mixed mark solution of gained
It is named as HB10.
Embodiment 11：Order of addition is ABCDEFHGIJKLMNOPQRSTUVWXY, the mixed mark solution of the gained of correspondence embodiment 3
It is named as HB11.
Embodiment 12：Order of addition is ABCDEFGIHJKLMNOPQRSTUVWXY, correspondence embodiment 4, the mixed mark solution of gained
It is named as HB12.
Embodiment 13：Order of addition is ABCDEFGHJIKLMNOPQRSTUVWXY, correspondence embodiment 1, the mixed mark solution of gained
It is named as HB13.
Embodiment 14：Order of addition is ABCDEFGHIKJLMNOPQRSTUVWXY, correspondence embodiment 2, the mixed mark solution of gained
It is named as HB14.
Embodiment 15：Order of addition is ABCDEFGHIJLKMNOPQRSTUVWXY, correspondence embodiment 3, the mixed mark solution of gained
It is named as HB15.
Embodiment 16：Order of addition is ABCDEFGHIJKMLNOPQRSTUVWXY, correspondence embodiment 4, the mixed mark solution of gained
It is named as HB16.
Embodiment 17：Order of addition is ABCDEFGHIJKLNMOPQRSTUVWXY, correspondence embodiment 1, the mixed mark solution of gained
It is named as HB17.
Embodiment 18：Order of addition is ABCDEFGHIJKLMONPQRSTUVWXY, correspondence embodiment 2, the mixed mark solution of gained
It is named as HB18.
Embodiment 19：Order of addition is ABCDEFGHIJKLMNPOQRSTUVWXY, correspondence embodiment 3, the mixed mark solution of gained
It is named as HB19.
Embodiment 20：Order of addition is ABCDEFGHIJKLMNOQPRSTUVWXY, correspondence embodiment 4, the mixed mark solution of gained
It is named as HB20.
Embodiment 21：Order of addition is ABCDEFGHIJKLMNOPRQSTUVWXY, correspondence embodiment 1, the mixed mark solution of gained
It is named as HB21.
Embodiment 22：Order of addition is ABCDEFGHIJKLMNOPQSRTUVWXY, correspondence embodiment 2, the mixed mark solution of gained
It is named as HB22.
Embodiment 23：Order of addition is ABCDEFGHIJKLMNOPQRTSUVWXY, correspondence embodiment 3, the mixed mark solution of gained
It is named as HB23.
Embodiment 24：Order of addition is ABCDEFGHIJKLMNOPQRSUTVWXY, correspondence embodiment 4, the mixed mark solution of gained
It is named as HB24.
Embodiment 25：Order of addition is ABCDEFGHIJKLMNOPQRSTVUWXY, correspondence embodiment 1, the mixed mark solution of gained
It is named as HB25.
Embodiment 26：Order of addition is ABCDEFGHIJKLMNOPQRSTUWVXY, correspondence embodiment 2, the mixed mark solution of gained
It is named as HB26.
Embodiment 27：Order of addition is ABCDEFGHIJKLMNOPQRSTUVXWY, correspondence embodiment 3, the mixed mark solution of gained
It is named as HB27.
Embodiment 28：Order of addition is ABCDEFGHIJKLMNOPQRSTUVWYX, correspondence embodiment 4, the mixed mark solution of gained
It is named as HB28.
Embodiment 29-31：Standard mixes the preparation of mark solution
Embodiment 29：The PEG-200 solution in step S2 is not added in step s3, and other are same as Example 1 (i.e.
Do not add stabilizer I), the mixed mark solution of gained is named as HB29.
Embodiment 30：The tetraethylene glycol solution in step S2 is not added in step s3, and other are same as Example 1 (i.e.
Do not add stabilizer II), the mixed mark solution of gained is named as HB30.
Embodiment 31：Do not add the PEG-200 solution and tetraethylene glycol solution in step S2 in step s3, other with
Embodiment 1 is identical (not adding stabilizer I and II), and the mixed mark solution of gained is named as HB31.
Embodiment 32-43：Standard mixes the preparation of mark solution
Embodiment 32-34：In addition to stabilizer I is replaced with into PEG-400, PEG-600 and PEG-800 by PEG-200 respectively,
Other operations are constant, and are carried out a 32-34 with the same way with embodiment 1, and the mixed mark solution of gained is sequentially named
It is HB32, HB33 and HB34.
Embodiment 35-37：In addition to stabilizer I is replaced with into PEG-400, PEG-600 and PEG-800 by PEG-200 respectively,
Other operations are constant, and are carried out a 35-37 with the same way with embodiment 2, and the mixed mark solution of gained is sequentially named
It is HB35, HB36 and HB37.
Embodiment 38-40：In addition to stabilizer I is replaced with into PEG-400, PEG-600 and PEG-800 by PEG-200 respectively,
Other operations are constant, and are carried out a 38-40 with the same way with embodiment 3, and the mixed mark solution of gained is sequentially named
It is HB38, HB39 and HB40.
Embodiment 41-43：In addition to stabilizer I is replaced with into PEG-400, PEG-600 and PEG-800 by PEG-200 respectively,
Other operations are constant, and are carried out a 41-43 with the same way with embodiment 4, and the mixed mark solution of gained is sequentially named
It is HB41, HB42 and HB43.
Performance test
First, checking of the mixed mark solution of the present invention to standard singly mark solution
1st, 23 kinds of decomposable asymmetric choice nets aromatic amine solid list mark balance (μ g of sensibility reciprocal 1) in following table are weighed, and is configured to concentration
The standard singly mark solution (i.e. concentration is 50ppm) of 50mg/L, is handed over using this 23 kinds of standard singly mark solutions with the mixed mark solution of the present invention
For the method for sample introduction, measured according to national standard normative testing method GB/T 17592-2011, so that using comprising 23 kinds
The mixed mark Solution H B1 (concentration of wherein each aromatic amine is 50ppm) of the gained of the embodiment of the present invention 1 of violated arylamine is to described
The concentration of 23 kinds of standard singly mark solutions verified, as a result see the table below 4.
Table 4：The mixed mark solution of the present invention and single mark concentration difference list
Note：" * " represents single mark concentration of wherein single mark concentration (ppm) of two kinds of materials of serial number 20,21 and checking
(ppm) 50 and 50.2 are respectively.
As seen from the above table, when being detected to detected sample using the mixed mark solution of standard of the invention, with very high
Precision, maximum verification error be only 0.8% (see sequence number 8).
2nd, when being verified to standard singly mark solution using the HB2-HB4 in embodiment 2-4 respectively, it is found that its precision is same
Sample is controlled in the range of maximum verification error≤0.8%, but for simplicity, is no longer arranged in table form one by one herein
Go out.
2nd, influence of the order of addition to testing result
In addition to being tested instead of HB1 using the HB5-HB28 of embodiment 5-28 respectively, other operation with above-mentioned " one "
It is identical, and make to verify standard singly mark solution, as a result find detect 5 kinds of following aromatic amines：
Additionally, the validation error of other aromatic amines is between 4-8%.
As can be seen here, the order of addition for mixing each aromatic amine in mark solution has significant shadow for final detection performance
When ringing, but changing the order of addition of any of which component, will all cause detection performance to be significantly reduced, cannot enter
Row high precision test.More seriously, having five kinds of aromatic amines cannot detect.
3rd, the influence of stabilizer
1st, in addition to being tested instead of HB1 using the HB29-HB30 of embodiment 29-30 respectively, other with above-mentioned " one "
In it is identical, and standard singly mark solution is verified, find 2,4- diamino anisoles and 2,4- diaminotoluenes cannot be examined
Go out, and 4,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl sulfide, ortho-aminotoluene, 2,4,5- trimethylbenzene aniline and adjacent ammonia
The validation error of base methyl phenyl ethers anisole is very high, between 15-20%.
2nd, in addition to being tested instead of HB1 using the HB31 of embodiment 31, other are identical with " one ", and to standard list
Mark solution is verified that discovery 2,4- diamino anisoles and 2,4- diaminotoluene cannot be detected, and 4,4 '-diaminourea two
Certain in phenylate, 4,4 '-diaminodiphenyl sulfide, ortho-aminotoluene, 2,4,5- trimethylbenzenes aniline and o-aminoanisole is several
Validation error further increase, see the table below：
As can be seen here, when stabilizer I and/or stabilizer II is added without, the detection performance of mixed mark solution is further reduced,
Thus demonstrate and only add stabilizer I and stabilizer II simultaneously, best, very excellent detection performance and effect could be obtained
Really.
4th, the influence of stabilizer I
1st, in addition to being tested instead of HB1 using the HB32-HB34 of embodiment 32-34 respectively, other with above-mentioned " one "
In it is identical, and standard singly mark solution is verified.Result find 2,4- diamino anisoles, 2,4 di amino toluene, 4,
4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl sulfide, ortho-aminotoluene, 2,4,5- trimethylbenzenes aniline and o-aminoanisole
Validation error between 1.5-2.4%.
2nd, in addition to replacing HB1 using HB35-43 and being tested, other are identical with above-mentioned " one ", and to standard list mark
Solution is verified.Result find 2,4- diamino anisoles, 2,4 di amino toluene, 4,4 '-diaminodiphenyl ether, 4,
The validation error of 4 '-diaminodiphenyl sulfide, ortho-aminotoluene, 2,4,5- trimethylbenzenes aniline and o-aminoanisole also between
Between 1.5-2.4%.
As can be seen here, for stabilizer I, not all of polyethylene glycol can have excellent Detection results, and
It is that in PEG-200, PEG-400, PEG-600 and PEG-800, PEG-200 has best effect.
As described above, the invention provides a kind of mixed mark solution and its preparation side of standard of aromatic amine detection in textile
Method, in the preparation method, by the factor such as the selection and use of specified stabiliser, the specific order of addition of all kinds of aromatic amines
Synergistic combination/effect, so as to obtained with excellent sensitivity and detection coverage rate mixed mark solution, can be used for textile neck
In the detection of the violated aromatic amine in domain, with good industrial applications potentiality and application prospect.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit protection model of the invention
Enclose.Additionally, it will also be appreciated that after technology contents of the invention have been read, those skilled in the art can make each to the present invention
Plant and change, change and/or modification, all these equivalent form of value equally falls within the guarantor that the application appended claims are limited
Within the scope of shield.
Claims (5)
1. aromatic amine detection standard mixes the preparation method of mark solution in a kind of textile, and methods described comprises the following steps：
S1：Prepare 23 kinds of singly mark solutions of aromatic amine；
S2：Prepare stabilizer I solution and stabilizer II solution；
S3：Prepare the mixed mark solution of the standard；
The step S1 is specially：23 kinds of aromatic amine compounds are weighed respectively, is dissolved into ultra-pure water, and carry out constant volume, obtain
The singly mark solution of every kind of aromatic amine, 23 kinds of aromatic amines are following aromatic amine compound：
The step S2 is specially：Stabilizer I and stabilizer II is weighed respectively, is dissolved in ultra-pure water, so as to obtain quality
Percent concentration is stabilizer I solution and stabilizer II solution in the range of 0.5-1.5%；
In step s 2, the stabilizer I is polyethylene glycol 200, PEG400, Macrogol 600 or polyethylene glycol-800；
In step s 2, the stabilizer II is tetraethylene glycol；
The step S3 is specially：Respectively each singly mark solution in removing step S1, the stabilizer I solution in step S2 with it is steady
Determine agent II solution, and be added mixing in particular order, then use acetonitrile constant volume, it is molten so as to obtain the mixed mark of the standard
Liquid；
In step s3, the specific order is as follows：
2. preparation method as claimed in claim 1, it is characterised in that：In step s 2, the stabilizer I is polyethylene glycol
200。
3. preparation method as claimed in claim 1 or 2, it is characterised in that：In step s3, stabilizer I solution is pipetted
The volume of volume and pipetted stabilizer II solution is 1 with the ratio of the cumulative volume of all pipetted singly mark solutions:500-1500.
4. the mixed mark of aromatic amine detection standard is molten in the textile that preparation method described in any one of claim 1-3 is prepared
Liquid.
5. the mixed mark solution of aromatic amine detection standard in the textile that preparation method described in any one of claim 1-3 is prepared
Purposes in the violated aromatic amine detection of textile.
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| CN110161134B (en) * | 2018-03-26 | 2022-03-18 | 厦门纽克泰生物技术有限公司 | Method for detecting nucleic acid solid sample methylamine and methylamine salt solvent residue |
| CN110749671A (en) * | 2019-10-21 | 2020-02-04 | 晋江中纺标检测有限公司 | Method for detecting decomposable aromatic amine dye in textile |
| CN113189220A (en) * | 2021-04-16 | 2021-07-30 | 佛山中纺联检验技术服务有限公司 | Rapid detection method of azo dye product |
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