1、September 2016 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 59.080.01!%ZQ“2559646www.din.de
2、DIN EN ISO 17881-2Textiles Determination of certain flame retardants Part 2: Phosphorus flame retardants (ISO 17881-2:2016);English version EN ISO 17881-2:2016,English translation of DIN EN ISO 17881-2:2016-09Textilien Bestimmung einiger Flammschutzmittel Teil 2: Phosphororganische Flammschutzmittel
3、 (ISO 17881-2:2016);Englische Fassung EN ISO 17881-2:2016,Englische bersetzung von DIN EN ISO 17881-2:2016-09Textiles Dtermination de certains retardateurs de flamme Partie 2: Retardateurs de flamme phosphors (ISO 17881-2:2016);Version anglaise EN ISO 17881-2:2016,Traduction anglaise de DIN EN ISO 1
4、7881-2:2016-09www.beuth.deDocument comprises 13 pagesDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.08.16 DIN EN ISO 17881-2:2016-09 2 A comma is used as the decimal marker. National foreword This document (EN ISO 17881-2:2016) has
5、 been prepared by Technical Committee ISO/TC 38 “Textiles” in collaboration with Technical Committee CEN/TC 248 “Textiles and textile products” (Secretariat: BSI, United Kingdom). The responsible German body involved in its preparation was DIN-Normenausschuss Materialprfung (DIN Standards Committee
6、Materials Testing), Working Committee NA 062-05-12 AA Textilchemische Prfverfahren und Fasertrennung. EN ISO 17881 consists of the following parts, under the general title Textiles Determination of certain flame retardants: Part 1: Brominated flame retardants Part 2: Phosphorus flame retardants EURO
7、PEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 17881-2 February 2016 ICS 59.080.01 English Version Textiles - Determination of certain flame retardants - Part 2: Phosphorus flame retardants (ISO 17881-2:2016) Textiles - Dtermination de certains retardateurs de flamme - Partie 2: Retardateurs d
8、e flamme phosphors (ISO 17881-2:2016) Textilien - Bestimmung einiger Flammschutzmittel - Teil 2: Phosphororganische Flammschutzmittel(ISO17881-2:2016) This European Standard was approved by CEN on 11 December 2015. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipu
9、late 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 Centre or to any CEN member. This European S
10、tandard 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 the official versions. CEN members are the
11、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, Netherlands, Norway, Poland, Portugal, Romania,
12、 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 2016 CEN All rights of exploitation in any form and by any
13、 means reserved worldwide for CEN national Members. Ref. No. EN ISO 17881-2:2016 EForeword 41 Scope .52 Principle 53 Reagents 54 Apparatus .55 Procedure.65.1 Preparation of standard solutions .65.1.1 Stock standard solution .65.1.2 Working solution .65.2 Preparation of test specimen 65.3 Ultrasonic
14、wave extraction .65.4 Flame retardants determination .66 Calculation 77 Test report .7Annex A (informative) Test parameters by HPLC-MS/MS .8Annex B (informative) Round Robin test 10Contents Page2EN ISO 17881-2:2016 (E) DIN EN ISO 17881-2:2016-09 European foreword .3European foreword This document (E
15、N ISO 17881-2:2016) has been prepared by Technical Committee ISO/TC 38 “Textiles” in collaboration with Technical Committee CEN/TC 248 “Textiles and textile products” the secretariat of which is held by BSI. This European Standard shall be given the status of a national standard, either by publicati
16、on of an identical text or by endorsement, at the latest by August 2016, and conflicting national standards shall be withdrawn at the latest by August 2016. 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
17、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 to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmar
18、k, 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 Kingdom. Endorsement noti
19、ce The text of ISO 17881-2:2016 has been approved by CEN as EN ISO 17881-2:2016 without any modification. 3EN ISO 17881-2:2016 (E) DIN EN ISO 17881-2:2016-09 ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). T
20、he work of preparing International Standards is normally carried out through ISO technical committees. Each member body 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-go
21、vernmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.The procedures used to develop this document and those intended for its further maintenance are described
22、in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted. This document was drafted in accordance with the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).Attention is drawn to the
23、possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of any patent rights identified during the development of the document will be in the Introduction and/or on the ISO li
24、st of patent declarations received (see www.iso.org/patents).Any trade name used in this document is information given for the convenience of users and does not constitute an endorsement.For an explanation on the meaning of ISO specific terms and expressions related to conformity assessment, as well
25、 as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary informationThe committee responsible for this document is ISO/TC 38, Textiles.ISO 17881 consists of the following parts, under the general title Textile
26、s Determination of certain flame retardants: Part 1: Brominated flame retardants Part 2: Phosphorus flame retardants4EN ISO 17881-2:2016 (E) DIN EN ISO 17881-2:2016-09 WARNING This International Standard calls for the use of substances and/or procedures that may be injurious to health if adequate pr
27、ecautions are not taken. It refers only to technical suitability and does not absolve the user from legal obligations relating to health and safety at any stage. It has been assumed in the drafting of this International Standard that the execution of its provisions is entrusted to appropriately qual
28、ified and experienced people.1 ScopeThis part of ISO 17881 specifies a test method for determining some phosphorous flame retardants in textiles by high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS).The method is applicable to all kinds of textile products.NOTE For tris (1-
29、aziridinyl) phosphineoxide (TEPA), only unbonded TEPA is extractable.2 PrincipleThe flame retardants are extracted from textile specimen by ultrasonic generator with acetone. The flame retardants in the specimen are identified and quantified by HPLC-MS/MS.3 ReagentsUnless otherwise specified, use on
30、ly reagents of recognized analytical grade.3.1 Tris (2,3-dibromopropyl) phosphate (TRIS), CAS no. 126-72-7.3.2 Tris (1-aziridinyl) phosphineoxide (TEPA), CAS no. 545-55-1.3.3 Tris (2-chloroethyl) phosphate (TCEP), CAS no. 115-96-8.3.4 Acetone.3.5 Acetonitrile (ACN).3.6 Ammonium acetate solution, 10
31、mmol/l.4 Apparatus4.1 High performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS).4.2 Ultrasonic generator, with a frequency from 35 kHz to 45 kHz.4.3 Evaporator device, with water bath at 40 C.5EN ISO 17881-2:2016 (E) DIN EN ISO 17881-2:2016-09 4.4 Glass vial, 40 ml with tight clos
32、ure.4.5 Flask, 100 ml.4.6 Filtration membrane, 0,45 m.4.7 Balance, an accuracy of 0,1 mg.5 Procedure5.1 Preparation of standard solutions5.1.1 Stock standard solutionPrepare 1 000 g/ml stock standard solutions of the individual flame retardant (3.1 to 3.3) in acetonitrile (3.5).5.1.2 Working solutio
33、nPrepare an admixture working solution of three flame retardants in acetonitrile and dilute it to a series of suitable concentrations depending on test needs. Select at least five appropriate dilutions of the calibration sets to create calibration curve and perform HPLC-MS/MS analysis.5.2 Preparatio
34、n of test specimenPrepare a representative test specimen of the sample. Cut it into small pieces and weigh (1,00 0,01) g of the pieces with a balance (4.7).5.3 Ultrasonic wave extractionPut the pieces into a vial with tight closure (4.4) and add 20 ml of acetone. Place the vial in an ultrasonic gene
35、rator (4.2) at 40 C for 40 min. Filter and transfer the extract into 100 ml flask (4.5). Add 20 ml of acetone to the residue and place the vial in the ultrasonic generator to extract the residue at 40 C for 20 min. Filter and merge the extract into the flask (4.5).Evaporate the extract to near dryne
36、ss by evaporator device (4.3). Add 2 ml of acetonitrile to dissolve the residue and then filter by filtration membrane (4.6). The filtrate is ready for determination of flame retardants.5.4 Flame retardants determinationDeterminate the flame retardants in solution (5.3) by HPLC-MS/MS (4.1). The test
37、 parameters by HPLC-MS/MS are given in Annex A as an example. Run a blank to control contamination.When the flame retardants level is very low, it is necessary to increase the mass of the pieces in order to reach at least three times the detection limit.When the flame retardant level is beyond the l
38、inear detector response range of the equipment, it is necessary to dilute the specimen liquid properly.6EN ISO 17881-2:2016 (E) DIN EN ISO 17881-2:2016-09 6 CalculationQuantify the concentration of each flame retardant by using the calibration curve. The content of each flame retardant is expressed
39、by the mass ratio of flame retardant to test specimen, in g/g. Calculate the result by using Formula (1).XCC Vmii=()0(1)whereXiis the content of the flame retardant, i, in the textile specimen, in g/g;Ciis the concentration of the flame retardant, i, in the specimen solution, in g/ml;C0is the concen
40、tration of the flame retardant, i, in the blank solution, in g/ml;V is the final volume of the specimen solution, in ml;m is the mass of the test specimen, in g.7 Test reportThe test report shall include the following information:a) a reference to this part of ISO 17881, i.e. ISO 17881-2:2016;b) all
41、 details necessary for identification of the sample tested;c) the content of each flame retardant;d) any deviation from the procedure specified.7EN ISO 17881-2:2016 (E) DIN EN ISO 17881-2:2016-09 Annex A (informative) Test parameters by HPLC-MS/MSA.1 Instrument parametersAs the instrumental equipmen
42、t of the laboratories may vary, no generally applicable parameters can be provided for chromatographic analyses. The following parameters have been found successfully.a) Eluent 1: 10 mmol/l ammonium acetate solution;b) Eluent 2: Acetonitrile;c) Chromatographic column: Pursuit XRs C18, 100 mm 2,0 mm,
43、 5 m;d) Column temperature: 30 C;e) Flow rate: 0,2 ml/min;f) Injection volume: 5,0 l;g) Gradient: Time (min) Eluent 2 (%) 0 10 3 70 10 80 12 95 17 95 17,1 10 25 10 h) Detection mode: Quadrupole tandem mass spectrometers;Multiple Reaction Monitoring (MRM);i) Ionizing mode: ESI electro spray ionizing
44、method and positive-ion detection;j) Impressed voltage: 5 500 V;k) Temperature of spray: 400 C;l) Spray gas: Nitrogen.A.2 Typical transitions and detection limitTypical transitions and detection limit for flame retardants are shown in Table A.1.8EN ISO 17881-2:2016 (E) DIN EN ISO 17881-2:2016-09 Tab
45、le A.1 Typical transitions and detection limitNo. Flame retardantPrecursor ion(m/z)Product ion(m/z)Detection limit(g/g)1 Tris (2,3-dibromopropyl) phosphate (TRIS) 698,699,1a1299,22 Tris (1-aziridinyl) phosphineoxide (TEPA) 174,0131,0a190,03 Tris (2-chloroethyl) phosphate (TCEP) 284,999,0163,0aaQuant
46、itative transition.9EN ISO 17881-2:2016 (E) DIN EN ISO 17881-2:2016-09 Annex B (informative) Round Robin testThe Round Robin test was carried out by five textile laboratories in China.A total of nine samples were prepared, three from cotton woven fabrics (no. 1 to 3), three from polyester woven fabr
47、ics (no. 4 to 6) and three from 50 cotton/50 polyester woven fabrics (no. 7 to 9) each containing three flame retardants, i.e. TRIS, TCEP, and TEPA. The three samples from each fabric were at three concentration levels of 10 mg/kg, 200 mg/kg, and 500 mg/kg. Three test specimens from each sample were
48、 tested in each laboratory.The results of the Round Robin test are shown in Table B.1.Table B.1 Results of the Round Robin testSample no.SubstanceExpected value(mg/kg)Mean(mg/kg)Recovery(%)Repeatability ReproducibilitySr(mg/kg) CVr(%) SR(mg/kg) CVR(%)1TRIS 10 8,59 85,90 0,35 4,08 0,32 3,71TCEP 10 8,
49、98 89,78 0,34 3,82 0,97 10,85TEPA 10 7, 53 75,27 0,27 3,58 1,54 20,442TRIS 200 189,56 94,78 13,02 6,87 20,98 11,07TCEP 200 194,92 97,46 9,52 4,88 18,44 9,46TEPA 200 206,04 103,02 15,73 7,6 4 14,84 7, 203TRIS 500 443,73 88,75 10,86 2,45 31,28 7,05TCEP 500 454,77 90,95 6,82 1,73 32,30 7,10TEPA 500 528,33 105,67 37,03 7,01 42,00 7,954TRIS 10 8,42 84,24 0,49 5,79 1,00 11,87TCEP 10 7,95 79,48 0,71 8,89 1,76 22,13TEPA 10 7,6 4 76,40 0,27 3,54 1,83 23,955TRIS
