1、November 2015 English price group 8No 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 59.140.30!%GNA“2364330www.din.de
2、DIN EN ISO 18218-1Leather Determination of ethoxylated alkylphenols Part 1: Direct method (ISO 18218-1:2015);English version EN ISO 18218-1:2015,English translation of DIN EN ISO 18218-1:2015-11Leder Bestimmung von ethoxylierten Alkylphenolen Teil 1: Direktes Verfahren (ISO 18218-1:2015);Englische F
3、assung EN ISO 18218-1:2015,Englische bersetzung von DIN EN ISO 18218-1:2015-11Cuir Dtermination chimique des alkylphnols thoxyls Partie 1: Mthode directe (ISO 18218-1:2015);Version anglaise EN ISO 18218-1:2015,Traduction anglaise de DIN EN ISO 18218-1:2015-11www.beuth.deDocument comprises 13 pagesDT
4、ranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.11.15 DIN EN ISO 18218-1:2015-11 2 A comma is used as the decimal marker. National foreword This document (EN ISO 18218-1:2015) has been prepared by Technical Committee CEN/TC 289 “Leath
5、er” (Secretariat: 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 0
6、62-05-52 AA Chemische Prfverfahren fr Leder. DIN EN ISO 18218 consists of the following parts, under the general title Leather Determination of ethoxylated alkylphenols: Part 1: Direct method Part 2: Indirect method The DIN Standards corresponding to the International Standards referred to in this d
7、ocument are as follows: ISO 2418 DIN EN ISO 2418 ISO 3696 DIN ISO 3696 ISO 4044 DIN EN ISO 4044 ISO 18218-2 DIN EN ISO 18218-2 National Annex NA (informative) Bibliography DIN EN ISO 2418, Leather Chemical, physical and mechanical and fastness tests Sampling location DIN EN ISO 4044, Leather Chemica
8、l tests Preparation of chemical test samples DIN EN ISO 18218-2, Leather Determination of ethoxylated alkylphenols Part 2: Indirect method DIN ISO 3696, Water for analytical laboratory use Specification and test methods EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 18218-1 June 2015 ICS 5
9、9.140.30 English Version Leather - Determination of ethoxylated alkylphenols - Part 1: Direct method (ISO 18218-1:2015) Cuir - Dtermination chimique des alkylphnols thoxyls - Partie 1: Mthode directe (ISO 18218-1:2015) Leder - Bestimmung von ethoxylierten Alkylphenolen - Teil 1: Direktes Verfahren (
10、ISO 18218-1:2015) This European Standard was approved by CEN on 28 February 2015. 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 alteration. Up-to-date lists and
11、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 made by translation under the re
12、sponsibility 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, Estonia, Finland, Former Yugoslav
13、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 United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE N
14、ORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2015 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 18218-1:2015 EContents Page European foreword . 3 Introduction 4
15、1 Scope 5 2 Normative references . 5 3 Principle 5 4 Apparatus and materials . 5 5 Chemicals 6 6 Sampling 6 7 Sample preparation and analysis 7 7.1 Extraction . 7 7.2 Analysis . 7 7.3 Calibration 7 7.4 Calculation 7 8 Test report 7 Annex A (informative) Chromatographic analysis operating parameters
16、9 Bibliography . 11 EN ISO 18218-1:2015 (E) DIN EN ISO 18218-1:2015-11 2 European foreword This document (EN ISO 18218-1:2015) has been prepared by Technical Committee CEN/TC 289 “Leather”, the secretariat of which is held by UNI, in collaboration with Technical Committee IULTCS “International Union
17、 of Leather Technologists 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 December 2015, and conflicting national standards shall be withdrawn at the latest by December 20
18、15. 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 for identifying any or all such patent rights. According to the CEN-CENELEC Internal Regulations, the national standards organiza
19、tions of the following countries are bound to implement this European Standard: 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, Mal
20、ta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. Endorsement notice The text of ISO 18218-1:2015 has been approved by CEN as EN ISO 18218-1:2015 without any modification. EN ISO 18218-1:2015 (E) DIN EN ISO 18218-1:2015
21、-11 3 IntroductionNonylphenol ethoxylate belongs to the non-ionic surfactants. The biodegradation of nonylphenol ethoxylate releases the persistent pollutant, the branched nonylphenol. Nonylphenol is a hormonal acting substance that is toxic for waterborne organisms and many other organisms. For thi
22、s reason the release of nonylphenol ethoxylate into the environment should be avoided.In 2003 the European Directive 2003/53/EC restricted the sale and use of nonylphenol and nonylphenol ethoxylate in product preparations for industries with discharges to waste water. Preparations containing concent
23、rations equal or higher than than 0,1 % of nonylphenol ethoxylate or nonylphenol were forbidden. This Directive is included as part of the EU Regulation 1907/2006 (REACH).No detailed composition of the chemical substance nonylphenol ethoxylate can be given, it is assigned the general structural form
24、ula:Calkylchain, branched or linear Ph -OCH CH -OHwit922n()hhPh=phenyl, n ()1 .To cover the group of ethoxylates of 4-nonylphenol, branched and linear, the European Chemical Agency (ECHA) has assigned the substance the following definition: 4-nonylphenol, branched and linear, ethoxylated substances
25、with a linear and/or branched alkyl chain with a carbon number of 9 covalently bound in position 4 to phenol, ethoxylated covering UVCB and well-defined substances, polymers and homologues, which include any of the individual isomers and/or combinations thereof.In the leather industry nonylphenol et
26、hoxylate and octylphenol ethoxylate surfactants have been used. However, the water insoluble substances, nonylphenol and octylphenol, have not been used. For this reason two different analytical procedures have been prepared for analysing leather samples.This part of ISO 18218 is a method that direc
27、tly determines the ethoxylated alkylphenol. It is an efficient procedure for the analysing of a larger number of leather samples. This procedure requires HPLC with triple quadrupole mass spectrometer (MSMS) to identify the nonylphenol ethoxylate and octylphenol ethoxylate.ISO 18218-2 is a procedure
28、for analysing the alkylphenol. The ethoxylated alkylphenol is cleaved to form the alkylphenol, which is identified using high-performance liquid chromatography (HPLC) or gas chromatography-mass spectrometry (GC-MS) equipment. This method can also be used to indirectly determine the alkylphenol ethox
29、ylate content in leather and process auxiliaries.EN ISO 18218-1:2015 (E) DIN EN ISO 18218-1:2015-11 4 1 ScopeThis part of ISO 18218 is a method for determining ethoxylated alkylphenols (nonyphenol ethoxylate NPEOnwith 1 n 16 and octylphenol ethoxylate OPEOnwith 1 n 16) in leather. This direct method
30、 is especially suitable where a larger number of leather samples are to be checked for the presence of ethoxylated alkylphenols.This method requires the use of high-performance liquid chromatography (HPLC) with triple quadrupole mass spectrometer (MSMS) to identify and quantify the ethoxylated alkyl
31、phenols.NOTE 1 In the leather industry, the most commonly used commercial ethoxylated alkylphenol is the NPEO with an average of 9 EO. It has an optimum cloud point in water for the typical leather processing temperatures of 40 C to 55 C.NOTE 2 ISO 18218-1 and ISO 18218-2 use different solvents for
32、the extraction of the ethoxylated alkylphenols from leather. Consequently, the two analytical methods are expected to give similar trends but not necessarily the same absolute result for the ethoxylated alkylphenol content in leather.2 Normative referencesThe following documents, in whole or in part
33、, 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 (including any amendments) applies.ISO 2418, Leather Chemical, physical and mechanical
34、and fastness tests Sampling locationISO 3696, Water for analytical laboratory use Specification and test methodsISO 4044, Leather Chemical tests Preparation of chemical test samples3 PrincipleThe leather sample is extracted in methanol using an ultrasonic bath. Subsequently, an aliquot of the soluti
35、on can, after filtering, be directly analysed without further cleaning of the sample using high-performance liquid chromatography (HPLC) with a triple quadrupole mass spectrometer (MSMS).4 Apparatus and materialsNormal laboratory apparatus and, in particular, the following:4.1 Ultrasonic bath, with
36、controllable heating capable of maintaining a temperature of (70 5) C.4.2 Glass container with a screw cap (22 ml has been found suitable).4.3 Polypropylene or polyethylene syringe, 2 ml.4.4 Syringe membrane filters, pore size 0,2 m, for use with syringe (4.3).EN ISO 18218-1:2015 (E) DIN EN ISO 1821
37、8-1:2015-11 5 4.5 Volumetric flasks, 10 ml and 100 ml.4.6 Analytical balance, weighing to 1 mg.4.7 Pipettes, various sizes, 1 ml to 5 ml.4.8 Instrumental equipment, high-performance liquid chromatograph with gradient elution and triple quadrupole mass spectrometer (HPLC-MSMS).5 ChemicalsIf not other
38、wise defined, analytical reagent grade chemicals shall be used.5.1 Methanol.5.2 Nonylphenol ethoxylate, NPEOnwith n = 9 10, CAS No. 68412-54-4, Sigma-AldrichProduct No. T9284 (IGEPALCO-630)1), technical grade.NOTE The brand name is given to improve the comparability of test results amongst laborator
39、ies. The commercial nonylphenol ethoxylate contains groups of ethoxylates of nonylphenol with linear and branched structures, so use of another reference can lead to different results. Only technical grade references are currently available from laboratory chemical suppliers.5.3 Octylphenol ethoxyla
40、te, OPEOnwith n = 9 10, CAS No. 9002-93-1, Sigma-AldrichProduct No. 542334 (Triton X-100)1), technical grade.NOTE The brand name is given to improve the comparability of test results amongst laboratories. The commercial octylphenol ethoxylate contains groups of ethoxylates of octylphenol with linear
41、 and branched structures, so use of another reference can lead to different results. Only technical grade references are currently available from laboratory chemical suppliers.5.4 Stock solution of nonylphenol ethoxylate and octylphenol ethoxylate, = 250 g/ml.25 mg of the respective alkylphenol etho
42、xylate (5.2 and 5.3) are dissolved in different 100 ml volumetric flasks (4.5) with methanol (5.1) and filled up to the mark.5.5 Calibration solutions of nonylphenol ethoxylate and octylphenol ethoxylateFour calibration solutions of = 2,5 g/ml, = 5 g/ml and = 10 g/ml and = 50 g/ml for each alkylphen
43、ol ethoxylate are prepared using the respective stock solution (5.4).5.6 Formic acid.5.7 Water, deionised or distilled water, grade 3 according to ISO 3696.6 SamplingThe sampling shall be made according to ISO 2418. If a sampling according to ISO 2418 is not possible (e.g. in case of leather from fi
44、nished products like shoes, clothing, etc.) the details of the sampling shall be given in the test report. Glue residuals shall be mechanically removed from leather samples.1) Sigma-AldrichProduct No. T9284 (IGEPALCO-630) and Sigma-AldrichProduct No. 542334 (Triton X-100) are examples of suitable pr
45、oducts available commercially. This information is given for the convenience of users of this document and does not constitute an endorsement by ISO or IDF of these products.EN ISO 18218-1:2015 (E) DIN EN ISO 18218-1:2015-11 6 The leather samples shall be cut into small pieces or ground according to
46、 ISO 4044. The dimensions of the pieces shall not be larger than 2 to 3 mm in size.7 Sample preparation and analysis7.1 ExtractionApproximately 1 g of the leather sample is weighed accurately to 10 mg in a screw-top glass container (4.2). 10 ml methanol (5.1) is added, the container closed and the s
47、ample extracted for (60 5) min in an ultrasonic bath (4.1) at (70 5) C.NOTE This method can also be used for analysing leather auxiliaries by the addition of the auxiliary to the screw-top container (4.2) instead of the leather sample. The auxiliary ought to be soluble in methanol or, if not, then t
48、he extraction solution ought to be centrifuged to give a clear extract.7.2 AnalysisAfter cooling down to room temperature, an aliquot of the extraction solution is removed using a disposable syringe (4.3) and transferred into an HPLC sample vial using a syringe filter (4.4). The aliquot is now ready
49、 for the HPLC analysis.The detection of the alkylphenol ethoxylate is made using an HPLC with gradient elution and triple quadrupole mass spectrometer (4.8). Guidelines for suitable chromatographic conditions are given in Annex A.7.3 CalibrationThe four calibration solutions (5.5) shall be transferred to an HPLC vial and analysed along with each batch of test samples. The peak areas of the fou
