DIN EN ISO 17234-2-2011 Leather - Chemical tests for the determination of certain azo colorants in dyed leathers - Part 2 Determination of 4-aminoazobenzene (ISO 17234-2 2011) Germ.pdf

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1、June 2011 Translation by DIN-Sprachendienst.English price group 12No 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!$s)j“1800671www.din.deDDIN EN ISO 17234-2Leather Chemical tests for the determination of certain azo colorants in dyedleathers Part 2: Determination of 4-aminoazobenzene (ISO 17234-2:2011)English translation of DIN EN ISO 17234-2:2011-06Leder Chemische Prfungen zur Bestimmung bestimmter Azo

3、farbstoffe in gefrbten Ledern Teil 2: Bestimmung von 4-Aminoazobenzol (ISO 17234-2:2011)Englische bersetzung von DIN EN ISO 17234-2:2011-06Cuir Essais chimiques pour le dosage de certains colorants azoques dans les cuirs teints Partie 2: Dosage du 4-aminoazobenzne (ISO 17234-2:2011)Traduction anglai

4、se de DIN EN ISO 17234-2:2011-06www.beuth.deDocument comprises pagesIn case of doubt, the German-language original shall be considered authoritative.2106.11 DIN EN ISO 17234-2:2011-06 2 A comma is used as the decimal marker. National foreword This standard has been prepared by Technical Committee CE

5、N/TC 289 “Leather” (Secretariat: UNI, Italy) in collaboration with the International Union of Leather Technologists and Chemists Societies. The responsible German body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Working Committee NA 062

6、-05-52 AA Chemische Prfverfahren fr Leder. EN ISO 17234 consists of the following parts, under the general title Leather Chemical tests for the determination of certain azo colorants in dyed leathers: Part 1: Determination of certain aromatic amines derived from azo colorants Part 2: Determination o

7、f 4-aminoazobenzene The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 2418 DIN EN ISO 2418 ISO 4044 DIN EN ISO 4044 National Annex NA (informative) Bibliography DIN EN ISO 2418, Leather Chemical, physical and mechanical and fastness tests

8、 Sampling location DIN EN ISO 4044, Leather Chemical tests Preparation of chemical test samples EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 17234-2 March 2011 ICS 59.140.30 English Version Leather - Chemical tests for the determination of certain azo colorants in dyed leathers - Part 2:

9、 Determination of 4-aminoazobenzene (ISO 17234-2:2011) Cuir - Essais chimiques pour le dosage de certains colorants azoques dans les cuirs teints - Partie 2: Dosage du 4-aminoazobenzne (ISO 17234-2:2011) Leder - Chemische Prfungen zur Bestimmung bestimmter Azofarbstoffe in gefrbten Ledern - Teil 2:

10、Bestimmung von 4-Aminoazobenzol (ISO 17234-2:2011) This European Standard was approved by CEN on 10 March 2011. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alt

11、eration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language ma

12、de 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 the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Esto

13、nia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EURO

14、PISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 17234-2:2011: EContents DIN EN ISO 17234-2:2011-06 EN ISO 17234-2:2011 (E) 2 Page Foreword3 1

15、Scope 4 2 Normative references 4 3 General4 4 Principle5 5 Safety precautions.5 6 Apparatus .5 7 Reagents.6 8 Sampling.6 9 Procedure .7 9.1 Degreasing .7 9.2 Reductive cleavage .7 9.3 Separation and concentration of 4-aminoazobenzene 7 9.4 Calibration solution .7 9.5 Check of the analytical system 8

16、 9.6 Chromatographic analyses.8 10 Evaluation.8 10.1 Calculation with internal standard.8 10.2 Calculation without internal standard .8 10.3 Reliability of the method .9 11 Test report 9 Annex A (informative) Chromatographic analyses10 Annex B (informative) Reliability of the method 17 Annex C (info

17、rmative) Assessment guide Interpretation of analytical results.18 Bibliography 19 Foreword This document (EN ISO 17234-2:2011:2011) has been prepared by Technical Committee CEN/TC 289 “Leather”, the secretariat of which is held by UNI, in collaboration with the International Union of Leather Technol

18、ogists and Chemists Societies. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by September 2011, and conflicting national standards shall be withdrawn at the latest by September 2011. Attention is d

19、rawn 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 for identifying any or all such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the follo

20、wing countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slova

21、kia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. DIN EN ISO 17234-2:2011-06 EN ISO 17234-2:2011 (E) 3 INTERNATIONAL STANDARD IULTCS/IUC 20-2:2011(E)1 Scope This part of ISO 17234 is supplementary to ISO 17234-1 and describes a special procedure to detect the use of certain azo color

22、ants in commodities, which can release 4-aminoazobenzene. The procedure also detects 4-aminoazobenzene (Solvent Yellow 1) which is already available as free amine in commodities without reducing pretreatment. Azo colorants that are able to form 4-aminoazobenzene generate, under the conditions of ISO

23、 17234-1, the amines aniline and 1,4-phenylenediamine. The presence of these 4-aminoazobenzene colorants cannot be reliably ascertained without additional information (e.g. the chemical structure of the colorant used) or without a special procedure. The use of certain azo colorants, which may releas

24、e, by reductive cleavage of their azo group(s), one or more of the other aromatic amines listed in Annex XVII of Regulation (EC) No. 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), except 4-aminoazobenzene,

25、cannot be determined quantitatively with this method. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (includi

26、ng any amendments) applies. ISO 2418, Leather Chemical, physical and mechanical and fastness tests Sampling location ISO 4044, Leather Chemical tests Preparation of chemical test samples 3 General Certain azo colorants may release by reductive cleavage of their azo group(s), 4-aminoazobenzene, which

27、 is proscribed under Annex XVII of Regulation (EC) No. 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH). Table 1 4-aminoazobenzene proscribed under Regulation REACH 1907/2006/Annex XVII No. CAS number Index nu

28、mber EC number Substance 22 60-09-3 611-008-00-4 200-453-6 4-aminoazobenzene DIN EN ISO 17234-2:2011-06 EN ISO 17234-2:2011 (E) 4 4 Principle After degreasing, the leather sample is treated with sodium dithionite in an alkaline solution at 40 C in a closed vessel. 4-Aminoazobenzene, which is release

29、d in the process, is transferred to a tert-butyl methyl ether phase by means of liquid/liquid extraction. An aliquot of the tert-butyl methyl ether phase is used for analysis. The detection and determination of 4-aminoazobenzene is performed using high-performance liquid chromatography (HPLC) with a

30、 diode array detector (DAD) or mass selective detector (HPLC/MS), capillary gas chromatography with a mass-selective detector (GC/MS) or capillary electrophoresis with a diode array detector (CE/DAD), or qualitatively with thin-layer chromatography (TLC, HPTLC). If 4-aminoazobenzene is detected by o

31、ne chromatographic method, confirmation shall be made using one or more alternative methods. Amine quantification is performed by HPLC/DAD. 5 Safety precautions 5.1 The compound 4-aminoazobenzene is classified as a substance suspected to be a human carcinogen. Any handling and disposal of this subst

32、ance shall be in strict accordance 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

33、recommendations. 5.3 Good laboratory practice should be followed. Wear safety glasses in all laboratory areas, and a dust respirator and single-use gloves while handling powder colorants and 4-aminoazobenzene. 5.4 Users should comply with any national and local safety regulations. 6 Apparatus Usual

34、laboratory equipment and, in particular, the following. 6.1 Suitable reaction vessel, of temperature-resistant glass with a gastight closure. 6.2 Heating source, that generates a temperature of (40 2) C. 6.3 Separator, with a revolution speed of more than 3 000 r/min. 6.4 Vacuum rotary evaporator. 6

35、.5 Pipettes, in required or variable sizes. 6.6 Ultrasonic bath, at least 160 W, with controllable heating. 6.7 Horizontal shaker, with a sufficient frequency of 5 s1, path length 2 cm to 5 cm. 6.8 Polypropylene or polyethylene syringe, 2 ml. 6.9 Instrumental equipment 6.9.1 Gas chromatography (GC),

36、 with mass-selective detector (MS). 6.9.2 High-performance liquid chromatography (HPLC), with gradient elution and diode array detector (DAD) or mass-selective detector (MS). DIN EN ISO 17234-2:2011-06 EN ISO 17234-2:2011 (E) 5 6.9.3 Thin-layer chromatography (TLC), or high-performance thin-layer ch

37、romatography (HPTLC) equipment, including relevant detection. 6.9.4 Capillary electrophoresis (CE) with DAD. NOTE A description of the equipment is given in Annex A. 7 Reagents Unless otherwise specified, analytical grade chemicals shall be used. 7.1 Sodium hydroxide. 7.2 Aqueous sodium dithionite s

38、olution, = 200 mg/ml1), freshly prepared, to be used immediately after resting for 1 h in a closed vessel. 7.3 Sodium hydroxide solution, w = 2 %2). 7.4 n-Hexane. 7.5 tert-Butyl methyl ether. 7.6 Sodium chloride. 7.7 4-Aminoazobenzene, highest purity. 7.8 Internal standards for gas chromatography (I

39、S), e.g.: IS1: naphthalene-d8 (CAS No.: 1146-65-2); IS2: 2,4,5-trichloroaniline (CAS No.: 636-30-6); IS3: benzidine-d8 (CAS No.: 92890-63-6); IS4: anthracene-d10 (CAS No.: 1719-06-8). 7.9 Standard solutions 7.9.1 Internal standard solution (IS), in tert-butyl methyl ether, = 10,0 g/ml. 7.9.2 4-Amino

40、azobenzene calibration solution, for checking the experimental procedure and preparation of calibration solutions, 4-aminoazobenzene in methanol, = 500 g/ml. 8 Sampling Sample in accordance with ISO 2418 and grind the leather in accordance with ISO 4044. If sampling in accordance with ISO 2418 is no

41、t possible (e.g. in the case of leathers from finished products like shoes, garments, etc.), details about sampling shall be given in the test report. Any traces of adhesives shall be removed mechanically. 1) = mass concentration 2) w = mass fraction (percentage by mass) DIN EN ISO 17234-2:2011-06 E

42、N ISO 17234-2:2011 (E) 6 In the case of leather patchwork fabrics with varicoloured patterns, the various colours have to be taken into account separately as far as possible. For commodities consisting of various leather qualities, specimens of the various qualities shall be analysed separately. 9 P

43、rocedure 9.1 Degreasing Treat more than 1,0 g of leather cut into pieces (25 mm2) or a ground leather sample in a closed 50 ml vessel (6.1) with 20 ml of n-hexane (7.4) in an ultrasonic bath (6.6) at (40 2) C for 20 min. Decant the n-hexane layer from the leather sample. Any loss of leather particle

44、s during decanting shall be avoided. Directly after decanting, treat the sample in the same way as before with 20 ml of n-hexane. Evaporate the residual n-hexane at least overnight in the open vessel. 9.2 Reductive cleavage Add 9 ml of sodium hydroxide solution (7.3) to the sample. Tightly close the

45、 reaction vessel and shake vigorously. All fibres of the leather material should be wetted. Subsequently, add 1,0 ml of the aqueous sodium dithionite solution (7.2) with a syringe (6.8). The sample and reduction solution is shaken vigorously and immediately kept at (40 2) C for exactly 30 min. Then

46、cool it to room temperature (20 C to 25 C) for 1 min with water or, if necessary, with a cooling mixture of ice, water and salt. 9.3 Separation and concentration of 4-aminoazobenzene Add 5 ml of tert-butyl methyl ether (7.5) or 5 ml of internal standard solution (7.9.1) to the reaction solution. Sub

47、sequently, add 7 g of sodium chloride (7.6) and shake the mixture constantly for 45 min; with a shaking frequency of f = 5 s1(6.7). For complete phase separation, centrifuge the mixture after shaking. The delay time between cooling down and shaking should not be longer than 5 min. For subsequent ana

48、lysis, transfer an aliquot of the tert-butyl methyl ether phase into an appropriate vial, which is closed immediately. Perform the detection and determination of 4-aminoazobenzene using the chromatographic techniques listed in 6.9. RECOMMENDATION For some analysis techniques, it may be necessary to

49、concentrate the extract from 9.3 or to transfer it to another appropriate solvent (e.g. methanol). It is recommended to concentrate the tert-butyl methyl ether extract to about 1 ml (not to dryness) in a rotary vacuum evaporator in a slight vacuum at not more than 50 C. Then remove the remainder of the solvent very carefully without vacuum by means of a weak flow of inert gas. NOTE 1 Removal of the solvent (concentration in the rotary vacuum evaporator, evaporation to dryness) can lead to substantial lo