1、November 2015 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 59.140.30!%GNB“2364331www.din.d
2、eDIN EN ISO 18218-2Leather Determination of ethoxylated alkylphenols Part 2: Indirect method (ISO 18218-2:2015);English version EN ISO 18218-2:2015,English translation of DIN EN ISO 18218-2:2015-11Leder Bestimmung von ethoxylierten Alkylphenolen Teil 2: Indirektes Verfahren (ISO 18218-2:2015);Englis
3、che Fassung EN ISO 18218-2:2015,Englische bersetzung von DIN EN ISO 18218-2:2015-11Cuir Dtermination chimique des alkylphnols thoxyls Partie 2 : Mthode indirecte (ISO 18218-2:2015);Version anglaise EN ISO 18218-2:2015,Traduction anglaise de DIN EN ISO 18218-2:2015-11www.beuth.deDocument comprises 20
4、 pagesDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.11.15 DIN EN ISO 18218-2:2015-11 2 A comma is used as the decimal marker. National foreword This document (EN ISO 18218-2:2015) has been prepared by Technical Committee CEN/TC 28
5、9 “Leather” (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 Commit
6、tee NA 062-05-52 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 i
7、n this document are as follows: ISO 2418 DIN EN ISO 2418 ISO 3696 DIN ISO 3696 ISO 4044 DIN EN ISO 4044 ISO 18218-1 DIN EN ISO 18218-1 ISO 18857-1 DIN EN ISO 18857-1 ISO 18857-2 DIN EN ISO 18857-2 National Annex NA (informative) Bibliography DIN EN ISO 2418, Leather Chemical, physical and mechanical
8、 and fastness tests Sampling location DIN EN ISO 4044, Leather Chemical tests Preparation of chemical test samples DIN EN ISO 18218-1, Leather Determination of ethoxylated alkylphenols Part 1: Direct method DIN EN ISO 18857-1, Water quality Determination of selected alkylphenols Part 1: Method for n
9、on-filtered samples using liquid-liquid extraction and gas chromatography with mass selective detection DIN EN ISO 18857-2, Water quality Determination of selected alkylphenols Part 2: Gas chromatographic-mass spectrometric determination of alkylphenols, their ethoxylates and bisphenol A in non-filt
10、ered samples following solid-phase extraction and derivatisation DIN ISO 3696, Water for analytical laboratory use Specification and test methods EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 18218-2 June 2015 ICS 59.140.30 English Version Leather - Determination of ethoxylated alkylpheno
11、ls - Part 2: Indirect method (ISO 18218-2:2015) Cuir - Dtermination chimique des alkylphnols thoxyls - Partie 2: Mthode indirecte (ISO 18218-2:2015) Leder - Bestimmung von ethoxylierten Alkylphenolen - Teil 2: Indirektes Verfahren (ISO 18218-2:2015) This European Standard was approved by CEN on 28 F
12、ebruary 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 bibliographical references concerning such national standards may be
13、 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 responsibility of a CEN member into its own language and notified to t
14、he 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 Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ir
15、eland, 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 NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management C
16、entre: 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 18218-2:2015 EContents Page European foreword . 3 Introduction 4 1 Scope 5 2 Normative references . 5 3 Principle 5 4 Apparatus and m
17、aterials . 6 5 Chemicals 6 6 Sampling and sample preparation . 7 6.1 Preparation of leather samples . 7 6.2 Preparation of leather process auxiliary samples 7 6.3 Blank determination . 8 6.4 Determination of OP and NP . 8 6.5 Determination of OPEO and NPEO 8 6.6 Chromatographic analysis . 9 6.7 Eval
18、uation . 9 7 Calibration 9 7.1 Calibration for OP and NP 9 7.2 Calibration for OPEO and NPEO . 9 8 Calculation 10 8.1 Calculation of OP and NP 10 8.2 Calculation of OPEO and NPEO . 10 9 Test report 11 Annex A (informative) Preparation of aluminium triiodide 12 Annex B (informative) Example of HPLC c
19、hromatograms 13 Annex C (informative) Example of GC-MS chromatograms 15 Bibliography . 1 8EN ISO 18218-2:2015 (E) DIN EN ISO 18218-2:2015-11 2 European foreword This document (EN ISO 18218-2:2015) has been prepared by Technical Committee CEN/TC 289 “Leather”, the secretariat of which is held by UNI,
20、 in collaboration with Technical Committee IULTCS “International Union 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 conflict
21、ing national standards shall be withdrawn at the latest by December 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 for identifying any or all such patent rights. According to
22、 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, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece
23、, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. Endorsement notice The text of ISO 18218-2:2015 has been approved by CEN as EN ISO 18218-2:2015 wit
24、hout any modification. EN ISO 18218-2:2015 (E) DIN EN ISO 18218-2:2015-11 3 IntroductionNonylphenol ethoxylate belongs to the non-ionic surfactants. The biodegradation of nonylphenol ethoxylate releases the persistent pollutant branched nonylphenol. Nonylphenol is a hormonal acting substance that is
25、 toxic for waterborne organisms and many other organisms. For this reason, the release of nonylphenol ethoxylate into the environment has to be avoided.In 2003, the European Directive 2003/53/EC restricted the sale and use of nonylphenol and nonylphenol ethoxylate in product preparations for industr
26、ies with discharges to waste water. Preparations containing concentrations equal or higher 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 ethox
27、ylate can be given; it is assigned the general structural formula:(C9alkyl chain, branched or linear) Ph OCH2CH2nOH (with Ph = 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:
28、 4-nonylphenol, branched and linear, ethoxylated substances 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/o
29、r combinations thereof.In the leather industry, nonylphenol ethoxylate 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 analysin
30、g leather samples.ISO 18218-1 is a method that directly 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 an
31、d octylphenol ethoxylate.This part of ISO 18218 is a procedure 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
32、 can also be used to indirectly determine the alkylphenol ethoxylate content in leather and process auxiliaries.EN ISO 18218-2:2015 (E) DIN EN ISO 18218-2:2015-11 4 1 ScopeThis part of ISO 18218 is a method for determining alkylphenols (nonylphenol and octylphenol) and alkylphenol ethoxylates (nonyl
33、phenol ethoxylate and octylphenol ethoxylate) in leather and process auxiliaries. The analysis is based on high-performance liquid chromatography (HPLC) or gas chromatography-mass spectrometry (GC-MS).The analysis of the alkylphenol ethoxylate is made by cleaving the alkylphenol ethoxylate and measu
34、ring the released alkylphenol.NOTE ISO 18218-1 and this part of ISO 18218 use different solvents for 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 ethoxyla
35、ted alkylphenol content in leather.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 refere
36、nced document (including 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 samples3 PrincipleLe
37、ather samples are extracted with acetonitrile using an ultrasonic bath and the nonylphenol (NP) and/or octylphenol (OP) in the extract is quantitatively determined by HPLC or GC-MS.The leather process auxiliaries are dissolved in acetonitrile and the NP and/or OP in the solution is quantitatively de
38、termined by HPLC or GC-MS.The nonylphenol ethoxylate (NPEO) and octylphenol ethoxylate (OPEO) in the extract or solution are first converted into NP and OP, using aluminium triiodide as cleavage agent, and the NP and OP are determined by HPLC or GC-MS. The contents of NPEO and OPEO are then calculat
39、ed by normalizing to NPEO9and OPEO10respectively. Examples of the four analytes used for the determination are shown in Table 1.Table 1 Analytes determinable by this methodAnalyte Empirical formula Abbreviation CASano.4-nonylphenol (mixture of isomers) C9H19-C6H4-OH NP 848521534-tert-octylphenol C8H
40、17-C6H4-OH OP 140669Nonylphenol ethoxylate C9H19-C6H4-(OC2H4)nOH (n9) NPEO99016459aCAS = Chemical Abstract Service.EN ISO 18218-2:2015 (E) DIN EN ISO 18218-2:2015-11 5 Analyte Empirical formula Abbreviation CASano.Octyphenol ethoxylate C8H17-C6H4-(OC2H4)nOH (n10) OPEO109002931aCAS = Chemical Abstrac
41、t Service.NOTE There are many CAS numbers for the nonylphenol ethoxylates and octylphenol ethoxylates. The CAS numbers in Table 1 are for the normalized structures used in the external calibration (see 7.2).4 Apparatus and materialsNormal laboratory apparatus and, in particular, the following:4.1 An
42、alytical balance, weighing to an accuracy of 0,1 mg.4.2 Ultrasonic bath, (40 2) kHz, with thermostat capable of maintaining a temperature of (50 5) C.4.3 Separating funnels, 150 ml.4.4 Rotary evaporator, with thermostat and vacuum system.4.5 Membrane filter, polyamide, 0,45 m.4.6 HPLC, equipped with
43、 diode array detector (DAD) or fluorescence detector (FLD).4.7 GC, equipped with mass selective detector (MSD).4.8 Filter paper, fast, quantitative.5 ChemicalsUnless otherwise stated, analytical grade chemicals shall be used.5.1 Acetonitrile, for HPLC.5.2 n-Hexane.NOTE Iso-hexane can also be used.5.
44、3 Aluminium triiodide, commercially available, or prepared according to Annex A.5.4 Sulfuric acid solution, 0,5 mol/L.5.5 Sodium thiosulfate solution, saturated at room temperature.5.6 Anhydrous magnesium sulfate (MgSO4), for analysis.5.7 Anhydrous sodium sulfate (Na2SO4), as desiccant for analysis.
45、 If not already an anhydrous powder, it can be treated at 800 C for 4 h, store dry.NOTE Other suitable desiccants can be used.5.8 Sodium chloride solution, saturated at room temperature.Table 1 (continued)EN ISO 18218-2:2015 (E) DIN EN ISO 18218-2:2015-11 6 5.9 NP (in Table 1) solution, for calibrat
46、ion, 1 000 mg/L in n-hexane.5.10 OP (in Table 1) solution, for calibration, 1 000 mg/L in n-hexane.5.11 OPEO (in Table 1) solution, for calibration, 2 000 mg/L in acetonitrile. Dilute this solution with acetonitrile (5.1) if a calibration is applied.5.12 NPEO (in Table 1) solution, for calibration,
47、4 000 mg/L in acetonitrile. Dilute this solution with acetonitrile (5.1) if a calibration is applied.5.13 4n-nonylphenol (4n-NP, CAS no. 104-40-5) solution, 1 000 mg/L in acetonitrile. The 4n-NP can be used as an internal standard for GC-MS analysis. Dilute this solution with acetonitrile (5.1) if t
48、he internal calibration curve is applied.5.14 Distilled or deionised water, according to ISO 3696:1987, Grade 3.6 Sampling and sample preparation6.1 Preparation of leather samples6.1.1 Sampling and preparation of samplesIf possible, sample the leather according to ISO 2418. Grind or cut the leather
49、in accordance with ISO 4044.If sampling in accordance with ISO 2418 is not possible (e.g. leathers from finished products like shoes, garments), details about the sampling shall be given in the test report.6.1.2 Sample extractionApproximately 2,5 g of the leather sample (6.1.1) is accurately weighed to 10 mg into an Erlenmeyer flask, mix with approximately 3 g of Na2SO4(5.7). Then add a (50,0 1) ml aliquot of
