© ISO 2016 Textiles — Determination of certain flame retardants — Part 2 Phosphorus flame retardants Textiles — Détermination de certains retardateurs de flamme — Partie 2 Retardateurs de flamme phosp[.]
INTERNATIONAL STANDARD ISO 17881-2 First edition 2016-02-01 Textiles — Determination of certain flame retardants — Part 2: Phosphorus flame retardants Textiles — Détermination de certains retardateurs de flamme — Partie 2: Retardateurs de flamme phosphorés Reference number ISO 17881-2:2016(E) © ISO 2016 ISO 17881-2:2016(E) COPYRIGHT PROTECTED DOCUMENT © ISO 2016, Published in Switzerland All rights reserved Unless otherwise specified, no part o f this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior written permission Permission can be requested from either ISO at the address below or ISO’s member body in the country o f the requester ISO copyright o ffice Ch de Blandonnet • CP 401 CH-1214 Vernier, Geneva, Switzerland Tel +41 22 749 01 11 Fax +41 22 749 09 47 copyright@iso.org www.iso.org ii © ISO 2016 – All rights reserved ISO 17881-2:2016(E) Contents Page Foreword iv Scope Principle Reagents Apparatus Procedure 5.1 5.2 5.3 Preparation of standard solutions 5.1.1 Stock standard solution 5.1.2 Working solution Preparation of test specimen Ultrasonic wave extraction Flame retardants determination Calculation Test report Annex A (informative) Test parameters by HPLC-MS/MS Annex B (informative) Round Robin test © ISO 2016 – All rights reserved iii ISO 7881 -2 : 01 6(E) Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies) The work o f 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-governmental, in liaison with ISO, also take part in the work ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters o f electrotechnical standardization The procedures used to develop this document and those intended for its further maintenance are described in the ISO/IEC Directives, Part In particular the different approval criteria needed for the di fferent types o f ISO documents should be noted This document was dra fted in accordance with the editorial rules of the ISO/IEC Directives, Part (see www.iso.org/directives) Attention is drawn to the possibility that some o f the elements o f this document may be the subject o f patent rights ISO shall not be held responsible for identi fying any or all such patent rights Details o f any patent rights identified during the development o f the document will be in the Introduction and/or on the ISO list of patent declarations received (see www.iso.org/patents) Any trade name used in this document is in formation given for the convenience o f users and does not constitute an endorsement For an explanation on the meaning o f ISO specific terms and expressions related to formity assessment, as well as information about ISO’s adherence to the WTO principles in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary in formation The committee responsible for this document is ISO/TC 38, Textiles 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 iv © ISO 2016 – All rights reserved INTERNATIONAL STANDARD ISO 17881-2:2016(E) Textiles — Determination o f certain flame retardants — Part 2: Phosphorus flame retardants WARNING — This International Standard calls for the use o f substances and/or procedures that may be injurious to health i f adequate precautions are not taken It re fers only to technical suitability and does not absolve the user from legal obligations relating to health and sa fety at any stage It has been assumed in the dra fting o f this International Standard that the execution o f its provisions is entrusted to appropriately qualified and experienced people Scope This part o f ISO 17881 specifies a test method for determining some phosphorous flame retardants in textiles by high per formance liquid chromatography – tandem mass spectrometry (HPLC-MS/MS) The method is applicable to all kinds of textile products NOTE For tris (1-aziridinyl) phosphineoxide (TEPA), only unbonded TEPA is extractable Principle The 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 Reagents Unless otherwise specified, use only reagents o f recognized analytical grade Tris (2 ,3 -dibromopropyl) phosphate (TRIS) Tris (1-aziridinyl) phosphineoxide 3 Tris (2 -chloroethyl) phosphate (TCEP) Acetone Acetonitrile (ACN) Ammonium acetate solution , CAS no 126-72-7 (TEPA) , CAS no 545-55-1 , CAS no 115-96-8 , 10 mmol/l Apparatus 4.1 High performance liquid chromatography – tandem mass spectrometry (HPLC-MS/MS) 4.2 Ultrasonic generator 4.3 Evaporator device , with a frequency from 35 kHz to 45 kHz , with water bath at 40 °C © ISO 2016 – All rights reserved ISO 7881 -2 : 01 6(E) , 40 ml with tight closure 4.4 Glass vial 4.5 Flask 4.6 Filtration membrane 4.7 Balance , 100 ml , 0,45 µm , an accuracy o f 0,1 mg Procedure 5 1 Preparation o f standard solutions Stock standard solution Prepare 000 μg/ml stock standard solutions o f the individual flame retardant (3.1 acetonitrile (3.5) to 3.3) in Working solution Prepare an admixture working solution o f three flame retardants in acetonitrile and dilute it to a series o f suitable concentrations depending on test needs Select at least five appropriate dilutions o f the calibration sets to create calibration curve and per form HPLC-MS/MS analysis Preparation o f test specimen Prepare 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 ) Ultrasonic wave extraction Put the pieces into a vial with tight closure (4.4) and add 20 ml of acetone Place the vial in an ultrasonic generator (4.2) at 40 °C for 40 Filter and trans fer 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 Filter and merge the extract into the flask (4.5 ) Evaporate the extract to near dryness by evaporator device (4.3 ) Add ml of acetonitrile to dissolve the residue and then filter by filtration membrane (4.6) The filtrate is ready for determination o f flame retardants Flame retardants determination Determinate the flame retardants in solution (5.3 ) by HPLC-MS/MS (4.1) The test 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 o f the pieces in order to reach at least three times the detection limit When the flame retardant level is beyond the linear detector response range o f the equipment, it is necessary to dilute the specimen liquid properly © ISO 2016 – All rights reserved ISO 17881-2:2016(E) Calculation Qua nti fy the concentration o f e ach fla me re tardant by u s i ng the c a l ibration c u r ve T he content o f e ach flame re tardant i s e xpre s s e d b y the mas s ratio o f flame re tardant to te s t s p e c i men, i n μg/g C a lc u late the re s u lt b y u s i ng Formu l a (1) Xi = ( Ci − C0 ) × V m (1) where Xi i s the content o f the fl ame re tardant, i, i n the te xti le s p e c i men, i n μg/g; Ci i s the concentration o f the fl ame re ta rd ant, i, i n the s p e c i men s olution, i n μg/m l; C i s the concentration o f the fl ame re ta rd ant, i, i n the bl an k s olution, i n μg/m l; V i s the fi na l volu me o f the s p e ci men s olution, i n m l; m is the mass of the test specimen, in g Test report The test report shall include the following information: a) a re ference to th i s p ar t o f I S O 178 81 , i e I S O 178 81-2 : 016; b) a l l de ta i l s ne ce s s a r y c) the content o f e ach flame re tardant; d) a ny deviation from for identi fic ation o f the s ample te s te d; the pro ce du re s p e c i fie d © ISO 2016 – All rights reserved ISO 17881-2:2016(E) Annex A (informative) Test parameters by HPLC-MS/MS A.1 Instrument parameters As the instrumental equipment o f the laboratories may vary, no generally applicable parameters can be provided for chromatographic analyses The following parameters have been found success fully a) b) c) d) e) f) g) Eluent 1: Eluent 2: Chromatographic column: Column temperature: Flow rate: Injection volume: Gradient: 10 mmol/l ammonium acetate solution; Acetonitrile; Pursuit XRs C18, 100 mm × 2,0 mm, μm; 30 °C; 0,2 ml/min; 5,0 μl; Time (min) 10 12 17 17,1 25 Eluent (%) 10 70 80 95 95 10 10 h) Detection mode: Quadrupole tandem mass spectrometers; Multiple Reaction Monitoring (MRM); i) Ionizing mode: Impressed voltage: ESI electro spray ionizing method and positive-ion detection; Temperature o f spray: 400 °C; Spray gas: Nitrogen j) k) l) A.2 500 V; Typical transitions and detection limit Typical transitions and detection limit for flame retardants are shown in Table A.1 © ISO 2016 – All rights reserved ISO 7881 -2 : 01 6(E) Table A.1 — Typical transitions and detection limit No a Flame retardant Precursor ion (m/z) Tris (2,3-dibromopropyl) phosphate (TRIS) 698,6 Tris (1-aziridinyl) phosphineoxide (TEPA) 174,0 Tris (2-chloroethyl) phosphate (TCEP) 284,9 Quantitative transition © ISO 2016 – All rights reserved Product ion (m/z) 99,1 a 299,2 131,0 a 90,0 99,0 63,0 a Detection limit (μg/g) 1 ISO 17881-2:2016(E) Annex B (informative) Round Robin test The 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 to 3), three from polyester woven fabrics (no to 6) and three from 50 cotton/50 polyester woven fabrics (no 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 tested in each laboratory The results of the Round Robin test are shown in Table B.1 Table B — Results o f the Round Robin test Sample no E xp ected Substance TRIS TCEP TEPA TRIS TCEP TEPA TRIS TCEP TEPA TRIS TCEP TEPA TRIS TCEP TEPA TRIS TCEP TEPA TRIS TCEP TEPA TRIS TCEP TEPA value (mg/ kg) 10 10 10 200 200 200 500 500 500 10 10 10 200 200 200 500 500 500 10 10 10 200 200 200 Repro ducibility Recovery (mg/ kg) (%) Sr (mg/kg) CVr (%) SR (mg/ kg) CVR (%) 8,59 8,98 85,90 89,78 0,35 4,08 0,32 3,71 10,85 7,53 189,56 194,92 206,04 443,73 454,77 528,33 8,42 7,95 7,64 176,51 188,70 204,53 437,35 456,61 475,22 8,04 8,52 7,36 183,53 200,93 185,82 75,27 94,78 97,46 103,02 88,75 90,95 105,67 84,24 79,48 76,40 88,26 94,35 102,27 0,34 0,27 13,02 9,52 15,73 10,86 6,82 37,03 42,00 11,07 9,46 7,20 7,05 7,10 7,95 20,77 0,28 4,55 3,69 21,43 0,37 5,71 7,05 5,05 3,11 3,51 2,86 7,45 8,18 13,13 0,40 91,76 100,46 92,91 1,73 7,01 31,28 32,30 20,44 2,78 5,21 3,51 0,71 0,27 85,24 73,60 4,88 7,64 2,45 0,97 1,54 20,98 18,44 14,84 11,87 22,13 12,68 80,36 3,82 3,58 6,87 1,00 1,76 1,83 15,53 11,37 12,71 0,49 87,47 91,32 95,04 NOTE The results of TEPA are from three laboratories Repeatability Mean 15,69 24,75 7,45 5,79 8,89 3,54 4,22 4,33 6,42 3,59 4,74 4,01 27,04 17,54 1,72 0,92 9,54 19,75 19,20 23,95 8,80 6,02 6,22 6,18 10,76 38,88 5,20 9,83 10,33 © ISO 2016 – All rights reserved ISO 17881-2:2016(E) Table B Sample no E xp ected Substance TRIS TCEP TEPA value (mg/kg) 500 500 500 Mean Recovery (mg/ kg) (%) 47 ,9 , 19 476 ,9 95 , 7, 4 101 ,49 NOTE The results of TEPA are from three laboratories © ISO 2016 – All rights reserved (continued) Repeatability Sr (mg/ kg) CVr (%) 13,70 15,60 36,68 2,88 3,27 7,23 Reproducibility SR (mg/kg) CVR (%) , 45 7, 52,00 21,05 ,9 4,1 ISO 7881 -2 : 01 6(E) ICS 59.080.01 Price based on pages © ISO 2016 – All rights reserved