BS EN ISO 17234-2-2011 Leather Chemical tests for the determination of certain azo colorants in dyed leathers Determination of 4-aminoazobenzene《皮革 皮革染色某种含氮色素的测定化学试验 4-氨基偶氮苯的测定》.pdf

1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN ISO 17234-2:2011Leather Chemical tests forthe determination of certainazo colorants in dyed leathersPart 2: Determination of 4-aminoazobenzene (ISO 17234-2:2011)BS EN ISO 1

2、7234-2:2011 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN ISO 17234-2:2011.The UK participation in its preparation was entrusted to Technical Committee TCI/69, Footwear, leather and coated fabrics.A list of organizations represented on this committee can be ob

3、tained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. BSI 2011 ISBN 978 0 580 67817 2 ICS 59.140.30Compliance with a British Standard cannot confer immunity from legal obligations

4、.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 March 2011.Amendments issued since publicationDate T e x t a f f e c t e dEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 17234-2 March 2011 ICS 59.140.30 English Version Leather -

5、Chemical tests for the determination of certain azo colorants in dyed leathers - Part 2: 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 -

6、Chemische Prfungen zur Bestimmung bestimmter Azofarbstoffe in gefrbten Ledern - Teil 2: 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 condit

7、ions 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 Centre or to any CEN member. This European Standard exists

8、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 the official versions. CEN members are the national standa

9、rds bodies of 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, Slovakia, Slovenia, Spain, Sweden, Switzerland and Un

10、ited Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES 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-

11、2:2011: EBS EN ISO 17234-2:2011EN ISO 17234-2:2011 (E) 3 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 Technologists and Chemists Socie

12、ties. 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 drawn to the possibility t

13、hat 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 following countries are bound

14、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, Slovakia, Slovenia, Spain, Swe

15、den, Switzerland and the United Kingdom. BS EN ISO 17234-2:2011ISO 17234-2:2011(E) IULTCS/IUC 20-2:2011(E) ISO 2011 All rights reserved iiiContents Page Foreword iv 1 Scope1 2 Normative references1 3 General .1 4 Principle .2 5 Safety precautions 2 6 Apparatus.2 7 Reagents 3 8 Sampling 3 9 Procedure

16、.4 9.1 Degreasing .4 9.2 Reductive cleavage .4 9.3 Separation and concentration of 4-aminoazobenzene4 9.4 Calibration solution.4 9.5 Check of the analytical system 5 9.6 Chromatographic analyses 5 10 Evaluation 5 10.1 Calculation with internal standard.5 10.2 Calculation without internal standard.5

17、10.3 Reliability of the method.6 11 Test report6 Annex A (informative) Chromatographic analyses .7 Annex B (informative) Reliability of the method14 Annex C (informative) Assessment guide Interpretation of analytical results 15 Bibliography16 BS EN ISO 17234-2:2011ISO 17234-2:2011(E) IULTCS/IUC 20-2

18、:2011(E) iv ISO 2011 All rights reservedForeword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member bo

19、dy interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrot

20、echnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adopted b

21、y the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent ri

22、ghts. ISO shall not be held responsible for identifying any or all such patent rights. ISO 17234-2 was prepared by the European Committee for Standardization (CEN) Technical Committee CEN/TC 289, Leather, in collaboration with the Chemical Test Commission of the International Union of Leather Techno

23、logists and Chemists Societies (IUC Commission, IULTCS), in accordance with the Agreement on technical cooperation between ISO and CEN (Vienna Agreement). This method is technically similar to the method in IUC 20-2. IULTCS, originally formed in 1897, is a world-wide organization of professional lea

24、ther societies to further the advancement of leather science and technology. IULTCS has three Commissions, which are responsible for establishing international methods for the sampling and testing of leather. ISO recognizes IULTCS as an international standardizing body for the preparation of test me

25、thods for leather. 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 of 4-aminoazobenzene BS EN I

26、SO 17234-2:2011INTERNATIONAL STANDARD ISO 17234-2:2011(E)IULTCS/IUC 20-2:2011(E) ISO 2011 All rights reserved 1Leather Chemical tests for the determination of certain azo colorants in dyed leathers Part 2: Determination of 4-aminoazobenzene 1 Scope This part of ISO 17234 is supplementary to ISO 1723

27、4-1 and describes a special procedure to detect the use of certain azo colorants 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 t

28、hat are able to form 4-aminoazobenzene generate, under the conditions of ISO 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 wit

29、hout a special procedure. The use of certain azo colorants, which may release, 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, Au

30、thorisation and Restriction of Chemicals (REACH), except 4-aminoazobenzene, 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. Fo

31、r undated references, the latest edition of the referenced document (including 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 r

32、elease by reductive cleavage of their azo group(s), 4-aminoazobenzene, which 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 pr

33、oscribed under Regulation REACH 1907/2006/Annex XVII No. CAS number Index number EC number Substance 22 60-09-3 611-008-00-4 200-453-6 4-aminoazobenzene BS EN ISO 17234-2:2011ISO 17234-2:2011(E) IULTCS/IUC 20-2:2011(E) 2 ISO 2011 All rights reserved4 Principle After degreasing, the leather sample is

34、 treated with sodium dithionite in an alkaline solution at 40 C in a closed vessel. 4-Aminoazobenzene, which is released 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 d

35、etection and determination of 4-aminoazobenzene is performed using high-performance liquid chromatography (HPLC) with a 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

36、 detector (CE/DAD), or qualitatively with thin-layer chromatography (TLC, HPTLC). If 4-aminoazobenzene is detected by one 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-a

37、minoazobenzene is classified as a substance suspected to be a human carcinogen. Any handling and disposal of this substance 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 ma

38、terials in this test method. Consult manufacturers for specific details, such as material safety data sheets and other 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 colo

39、rants and 4-aminoazobenzene. 5.4 Users should comply with any national and local safety regulations. 6 Apparatus Usual 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 te

40、mperature of (40 2) C. 6.3 Separator, with a revolution speed of more than 3 000 r/min. 6.4 Vacuum rotary evaporator. 6.5 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

41、 cm to 5 cm. 6.8 Polypropylene or polyethylene syringe, 2 ml. 6.9 Instrumental equipment 6.9.1 Gas chromatography (GC), 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). BS EN

42、ISO 17234-2:2011ISO 17234-2:2011(E) IULTCS/IUC 20-2:2011(E) ISO 2011 All rights reserved 36.9.3 Thin-layer chromatography (TLC), or high-performance thin-layer chromatography (HPTLC) equipment, including relevant detection. 6.9.4 Capillary electrophoresis (CE) with DAD. NOTE A description of the equ

43、ipment 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 solution, = 200 mg/ml1), freshly prepared, to be used immediately after resting for 1 h in a closed vessel. 7.3 Sodium hydroxide solution,

44、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 (IS), 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-

45、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-Aminoazobenzene calibration solution, for checking the experimental procedure and preparation of calibration solutions, 4-aminoazobenzene in me

46、thanol, = 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 not possible (e.g. in the case of leathers from finished products like shoes, garments, etc.), details about sampling shall be given in the

47、test report. Any traces of adhesives shall be removed mechanically. 1) = mass concentration 2) w = mass fraction (percentage by mass) BS EN ISO 17234-2:2011ISO 17234-2:2011(E) IULTCS/IUC 20-2:2011(E) 4 ISO 2011 All rights reservedIn the case of leather patchwork fabrics with varicoloured patterns, t

48、he 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 Procedure 9.1 Degreasing Treat more than 1,0 g of leather cut into pieces (25 mm2) or a ground l

49、eather 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 particles 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 reac