DIN EN ISO 17234-1-2015 Leather - Chemical tests for the determination of certain azo colorants in dyed leathers - Part 1 Determination of certain aromatic amines derived from azo .pdf

1、July 2015 Translation by DIN-Sprachendienst.English price group 11No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 5

2、9.140.30!%CwQ“2328446www.din.deDDIN EN ISO 17234-1Leather Chemical tests for the determination of certain azo colorants in dyedleathers Part 1: Determination of certain aromatic amines derived from azocolorants (ISO 17234-1:2015);English version EN ISO 17234-1:2015,English translation of DIN EN ISO

3、17234-1:2015-07Leder Chemische Prfungen zur Bestimmung bestimmter Azofarbstoffe in gefrbten Ledern Teil 1: Bestimmung bestimmter aromatischer Amine aus Azofarbstoffen(ISO 17234-1:2015);Englische Fassung EN ISO 17234-1:2015,Englische bersetzung von DIN EN ISO 17234-1:2015-07Cuir Essais chimiques pour

4、 le dosage de certains colorants azoques dans les cuirs teints Partie 1: Dosage de certaines amines aromatiques drives des colorants azoques(ISO 17234-1:2015);Version anglaise EN ISO 17234-1:2015,Traduction anglaise de DIN EN ISO 17234-1:2015-07SupersedesDIN EN ISO 17234-1:2010-06www.beuth.deDocumen

5、t comprises 20 pagesIn case of doubt, the German-language original shall be considered authoritative.06.15 DIN EN ISO 17234-1:2015-07 2 A comma is used as the decimal marker. National foreword This document (EN ISO 17234-1:2015) has been prepared by Technical Committee CEN/TC 289 “Leather” (Secretar

6、iat: UNI, Italy) in collaboration with the International Union of Leather Technologists and Chemists Societies (IULTCS). The responsible German body involved in its preparation was the DIN-Normenausschuss Materialprfung (DIN Standards Committee Materials Testing), Working Committee NA 062-05-52 AA C

7、hemische Prfverfahren fr Leder. The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 2418 DIN EN ISO 2418 ISO 3696 DIN ISO 3696 ISO 4044 DIN EN ISO 4044 ISO 17234-2 DIN EN ISO 17234-2 Amendments This standard differs from DIN EN ISO 17234-1:

8、2010-06 as follows: a) two new aromatic amines have been included in Table 1; b) reference to the Chinese Standard GB 20400-2006 has been included; c) the standard has been editorially revised. Previous editions DIN ISO/TS 17234: 2004-01 DIN EN ISO 17234-1: 2010-06 National Annex NA (informative) Bi

9、bliography DIN EN ISO 2418, Leather Chemical, physical and mechanical and fastness tests Sampling location DIN EN ISO 4044, Leather Chemical tests Preparation of chemical test samples DIN EN ISO 17234-2, Leather Chemical tests for the determination of certain azo colorants in dyed leathers Part 2: D

10、etermination of 4-aminoazobenzene DIN ISO 3696, Water for analytical laboratory use Specification and test methods EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 17234-1 April 2015 ICS 59.140.30 Supersedes EN ISO 17234-1:2010English Version Leather - Chemical tests for the determination of

11、 certain azo colorants in dyed leathers - Part 1: Determination of certain aromatic amines derived from azo colorants (ISO 17234-1:2015)Cuir - Essais chimiques pour le dosage de certains colorants azoques dans les cuirs teints - Partie 1: Dosage de certaines amines aromatiques drives des colorants a

12、zoques (ISO 17234-1:2015) Leder - Chemische Prfungen zur Bestimmung bestimmter Azofarbstoffe in gefrbten Ledern - Teil 1: Bestimmung bestimmter aromatischer Amine aus Azofarbstoffen17234-1:2015) This European Standard was approved by CEN on 14 February 2015. CEN members are bound to comply with the

13、CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management

14、Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as

15、 the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Net

16、herlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2015 CEN All r

17、ights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 17234-1:2015 E(ISO Contents PageForeword 31 Scope . 42 Normative references 43 General 44 Principle 55 Safety precautions 66 Apparatus . 67 Reagents 78 Sampling and preparation of samples

18、 89 Procedure. 89.1 Degreasing 89.2 Reductive cleavage . 89.3 Liquid-liquid extraction 89.4 Check of the analytical system . 910 Chromatographic analyses . 911 Calibration 912 Evaluation 912.1 Calculation of amine in the sample . 912.2 Reliability of the method . 1013 Test report 10Annex A (informa

19、tive) Chromatographic analyses . 11Annex B (informative) Reliability of the method 15Annex C (informative) Assessment guide Interpretation of analytical results .16Bibliography .18DIN EN ISO 17234-1:2015-07 EN ISO 17234-1:2015 (E) 2 Foreword This document (EN ISO 17234-1:2015) has been prepared by I

20、ULTCS “International Union of Leather Technologists and Chemists Societies“ in collaboration with Technical Committee CEN/TC 289 “Leather” the secretariat of which is held by UNI. This European Standard shall be given the status of a national standard, either by publication of an identical text or b

21、y endorsement, at the latest by October 2015, and conflicting national standards shall be withdrawn at the latest by October 2015. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible fo

22、r identifying any or all such patent rights. This document supersedes EN ISO 17234-1:2010. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Cz

23、ech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingd

24、om. Endorsement notice The text of ISO 17234-1:2015 has been approved by CEN as EN ISO 17234-1:2015 without any modification. DIN EN ISO 17234-1:2015-07 EN ISO 17234-1:2015 (E) 3 1 ScopeThis part of ISO 17234 specifies a method for determining the use of certain azo colorants which can release certa

25、in aromatic amines.2 Normative referencesThe following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (i

26、ncluding any amendments) applies.ISO 2418, Leather Chemical, physical and mechanical and fastness tests Sampling locationISO 3696:1987, Water for analytical laboratory use Specification and test methodsISO 4044, Leather Chemical tests Preparation of chemical test samplesISO 17234-2, Leather Chemical

27、 tests for the determination of certain azo colorants in dyed leathers Part 2: Determination of 4-aminoazobenzene3 GeneralCertain azo colorants can release, by reductive cleavage of azo group(s), one or more of the following aromatic amines, which are listed in Appendix 8 of EU Regulation 1907/2006,

28、 Annex XVII of the European Parliament, and/or the Chinese Standard GB 20400-2006.Table 1 Aromatic amines listed in Appendix 8 of EU regulation 1907/2006, Annex XVII, and/or GB 204002006No. CAS number Index number EC number Substances1 92671 612072006 2021771 biphenyl-4-ylamine 4-aminobiphenyl xenyl

29、amine2 92875 612042002 2021991 benzidine3 95692 2024416 4-chloro-o-toluidine4 91598 612022003 2020804 2-naphthylamine5a97563 611006003 2025912 o-aminoazotoluene 4-amino-2,3-dimethyla-zobenzene 4-o-tolylazo-o-toluidine6a99558 2027658 5-nitro-o-toluidine7 106478 612137009 2034010 4-chloroanilineDIN EN

30、 ISO 17234-1:2015-07 EN ISO 17234-1:2015 (E) 4 No. CAS number Index number EC number Substances8 615054 2104061 4-methoxy-m-phenylenedi-amine9 101779 612051001 2029744 4,4-methylenedianiline 4,4-diaminodiphenylmeth-ane10 91941 612068004 2021090 3,3-dichlorobenzidine 3,3-dichlorobiphenyl-4,4-ylenedia

31、mine11 119904 61203600-X 2043554 3,3-dimethoxybenzidine o-dianisidine12 119937 612041007 2043580 3,3-dimethylbenzidine 4,4-bi-o-toluidine13 838880 612085007 2126588 4,4-methylenedi-o-tolui-dine14 120718 2044191 6-methoxy-m-toluidine p-cresidine15 101144 612078009 2029189 4,4-methylene-bis-(2-chloro-

32、aniline) 2,2-dichloro-4.4-methyl-ene-dianiline16 101804 2029770 4,4-oxydianiline17 139651 2053709 4,4-thiodianiline18 95534 61209100-X 2024290 o-toluidine 2-aminotoluene19 95807 612099003 2024531 4-methyl-m-phenylenedi-amine20 137177 2052820 2,4,5-trimethylaniline21 90040 612035004 2019631 o-anisidi

33、ne 2-methoxyaniline22b60093 611008004 2004536 4-aminoazobenzene23c95681 612027000 2024400 2,4-xylidine2,4-dimethylbenzene-1-amine24c87627 61216100-X 2017587 2,6-xylidine2,6-dimethylbenzene-1-amineaThe CAS-numbers 97563 (No. 5) and 99558 (No. 6) are further reduced to CAS-numbers 95534 (No. 18) and 9

34、5807 (No. 19).bAzo colorants that are able to form 4-aminoazobenzene, generate under the condition of this method aniline and/or 1,4-phenylenediamine. The presence of these colorants shall be tested using ISO 17234-2.cAdditional aromatic amines in the Chinese Standard GB 2040020064 PrincipleAfter de

35、greasing, the leather sample is treated with sodium dithionite in an aqueous buffer solution (pH 6) at 70 C in a closed vessel. The amines released in the process of reductive cleavage are transferred to a t-butyl methyl ether phase by means of liquid-liquid extraction using Kieselgur columns. The t

36、butyl methyl ether extract is then concentrated under mild conditions in a rotary vacuum evaporator and the residue is dissolved in a suitable solvent, depending on the method used to determine the amines.Table 1 (continued)DIN EN ISO 17234-1:2015-07 EN ISO 17234-1:2015 (E) 5 Determination of the a

37、mines is performed by means of high-peformance liquid chromatography (HPLC) using a diode array detector (DAD) or mass selective detector (HPLC/MS), capillary gas chromatography with a mass-selective detector (GC-MS) or by capillary electrophoresis with a diode array detector (CE/DAD), or qualitativ

38、ely with thin layer chromatography (TLC, HPTLC).The amines shall be identified by means of at least two different chromatographic separation methods in order to avoid any possible misinterpretations caused by interfering substances (such as position isomers of the amines to be identified) and hence

39、any incorrect statements. Amine quantification shall be performed by HPLC/DAD or GC/MS.5 Safety precautions5.1 WARNING The aromatic amines listed in Clause 3 are classified as substances known to be or suspected to be human carcinogens.Any handling and disposal of this substance shall be in strict a

40、ccordance with the appropriate national health and safety regulations.5.2 It is the users responsibility to use safe and proper techniques when handling materials in this test method. Consult manufacturers for specific details, such as material safety data sheets and other recommendations.5.3 Good l

41、aboratory practice should be followed. Wear safety glasses in all laboratory areas, and a dust respirator and single-use gloves while handling powder colorants and aromatic amines.5.4 Users should comply with any national and local safety regulations.6 ApparatusUsual laboratory equipment and, in par

42、ticular, the following:6.1 Suitable reaction vessel, of temperature-resistant glass with a gas-tight closure.6.2 Hot cabinet with sand bath (sea sand, 0,1 mm to 0,3 mm) or water bath with thermostat.6.3 Thermometer, 0,5 C accuracy at 70 C.6.4 Volumetric flasks, different volumes.6.5 Polypropylene or

43、 glass column 1)with 25 mm to 30 mm inner diameter and 140 mm to 150 mm length, glass filter at the outlet, filled with porous granulated Kieselgur.6.6 Polypropylene or polyethylene syringe, 2 ml.6.7 Vacuum rotary evaporator with vacuum control and water bath.6.8 Pipettes, 10 ml, 5 ml, 2 ml, 1 ml.6.

44、9 Ultrasonic bath with thermostat.1) The EXtrelut NT20 prefilled column supplied by Merck is an example of a suitable product available commercially. This information is given for the convenience of users of this part of ISO 17234 and does not constitute an endorsement by ISO of this product. Equiva

45、lent products can be used if they can be shown to lead to the same results.DIN EN ISO 17234-1:2015-07 EN ISO 17234-1:2015 (E) 6 6.10 Round-bottomed flask, of 100 ml with standard ground joint NS 29/32.6.11 Chromatographic equipment selected from the following:6.11.1 High performance liquid chromatog

46、raphy (HPLC) with gradient controller and DAD or MS detector.6.11.2 Capillary gas chromatography (GC) with mass selective detector (MS).6.11.3 Capillary electrophoresis (CE) with DAD.6.11.4 Thin layer chromatography (TLC) or high performance thin layer chromatogrphy (HPTLC).NOTE A description of the chromatographic equipment is given in Annex A.7 ReagentsUnless otherwise specified, analytical grade chemicals shall be used.7.1 Methanol.7.2 t-butyl methyl ether.7.3 Sodium dithionite, minimum 87 % purity (mass fraction).7.4 Aqueous