1、BSI Standards PublicationBS ISO 17257:2013Rubber Identification ofpolymers Pyrolytic gas-chromatographic method usingmass-spectrometric detectionBS ISO 17257:2013 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 17257:2013.The UK participation in its preparation
2、 was entrusted to TechnicalCommittee PRI/23, Test methods for rubber and non-blackcompounding ingredients.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are
3、 responsible for its correctapplication. The British Standards Institution 2014. Published by BSI StandardsLimited 2014ISBN 978 0 580 77262 7ICS 83.060Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandar
4、ds Policy and Strategy Committee on 28 February 2014.Amendments issued since publicationDate Text affectedBS ISO 17257:2013 ISO 2013Rubber Identification of polymers Pyrolytic gas-chromatographic method using mass-spectrometric detectionCaoutchouc Identification des polymres Mthode par pyrolyse et c
5、hromatographie en phase gazeuse avec dtection par spectromtrie de masseINTERNATIONAL STANDARDISO17257First edition2013-12-15Reference numberISO 17257:2013(E)BS ISO 17257:2013ISO 17257:2013(E)ii ISO 2013 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2013All rights reserved. Unless otherwise spe
6、cified, no part of 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
7、ISOs member body in the country of the requester.ISO copyright officeCase postale 56 CH-1211 Geneva 20Tel. + 41 22 749 01 11Fax + 41 22 749 09 47E-mail copyrightiso.orgWeb www.iso.orgPublished in SwitzerlandBS ISO 17257:2013ISO 17257:2013(E) ISO 2013 All rights reserved iiiContents PageForeword iv1
8、Scope . 12 Normative references 13 List of rubbers . 13.1 Group M . 13.2 Group O 23.3 Group Q 23.4 Group R 23.5 Rubber blends 24 Principle 25 Reagents 36 Equipment . 37 Operating conditions . 47.1 General . 47.2 Gas chromatograph adjustment . 47.3 Extraction 47.4 Test portion 47.5 Pyrolysis 48 Inter
9、pretation of results . 48.1 General . 48.2 Group M . 48.3 Group O 58.4 Group Q 58.5 Group R 59 Test report . 6Annex A (informative) Schematic diagram of the chromatographic equipment 8Annex B (informative) Examples of operating conditions . 9Annex C (informative) Chromatogram examples .10Annex D (in
10、formative) Chemical compounds identified in rubber pyrolysates .11BS ISO 17257:2013ISO 17257:2013(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally c
11、arried 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 wor
12、k. 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 in the ISO/IEC Directives, Part 1. In particular the diffe
13、rent 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 possibility that some of the elements of this document may
14、 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 list of patent declarations received (see www.iso.org/patent
15、s). 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 as information about ISOs adherence to the WTO principle
16、s in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary informationThe committee responsible for this document is ISO/TC 45, Rubber and rubber products, Subcommittee SC 2, Testing and analyses.iv ISO 2013 All rights reservedBS ISO 17257:2013INTERNATIONAL STANDARD I
17、SO 17257:2013(E)Rubber Identification of polymers Pyrolytic gas-chromatographic method using mass-spectrometric detection1 ScopeThis International Standard provides a qualitative method for the identification of rubbers by their pyrolysis products using tandem the gas-chromatography /mass spectromet
18、ry.The method applies to rubbers in the raw state and to unvulcanized and vulcanized compounds. Compounds can be based on a single rubber or a blend of two or more rubbers. Where the level of a particular rubber in a blend is 10 % detection and identification can be difficult.A non-restrictive list
19、of rubbers is given in Clause 3.2 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 reference
20、d document (including any amendments) applies.ISO 1407, Rubber Determination of solvent extractISO 1629, Rubber and latices Nomenclature3 List of rubbersThe following list is not restrictive.Rubbers are presented according to ISO 1629.3.1 Group M3.1.1 Chloropolyethylene (CM)3.1.2 Chlorosulfonylpolye
21、thylene (CSM)3.1.3 Ethylene-propylene copolymer (EPM) and Ethylene-propylene-diene terpolymer (EPDM)The method cannot distinguish between them.3.1.4 Fluorocarbon rubber having substituent fluoro, perfluoroalkyl, or perfluoroalkoxy groups on the polymer chain (FKM)The method cannot distinguish betwee
22、n them. ISO 2013 All rights reserved 1BS ISO 17257:2013ISO 17257:2013(E)3.2 Group O3.2.1 Homopolymer of epichlorhydrin (CO), copolymer of epichlorhydrin-ethylene oxide (ECO), terpolymer of epichlorhydrin-ethylene oxide-allyl glycidyl ether (GECO)The method cannot distinguish between them.3.3 Group Q
23、3.3.1 Polysiloxanes (MQ, VMQ, PVMQ)The method cannot distinguish MQ and VMQ, but can distinguish PVMQ from the two other polymers.3.4 Group R3.4.1 Butadiene rubber (BR)3.4.2 Chloroprene rubber (CR)3.4.3 Isobutene-isoprene rubber (IIR), chlorinated IIR (CIIR) and brominated IIR (BIIR)The method canno
24、t distinguish between them.3.4.4 Natural rubber (NR) and synthetic isoprene rubber (IR)The method cannot distinguish between them.3.4.5 Acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (HNBR) and carboxylated NBR (XNBR)The method can only distinguish HNBR from the two other polymers (NBR and X
25、NBR).3.4.6 Styrene-butadiene rubber (SBR)The method allows butadiene-methylstyrene rubber to be distinguished from butadiene-styrene rubber.3.5 Rubber blendsIn copolymer-homopolymer blends having one common monomer (e.g. SBR/BR, NBR/BR), the technique does not allow the homopolymer to be distinguish
26、ed.This is also valid for blends with terpolymers.4 Principle4.1 Raw rubbers, or vulcanized or unvulcanized compounds which previously have been solvent extracted, are pyrolysed and the pyrolysate analysed by gas chromatography with mass spectrometric detection.4.2 The interpretation of the results
27、is made by examining the mass spectra of the specific chromatographic peaks.2 ISO 2013 All rights reservedBS ISO 17257:2013ISO 17257:2013(E)5 ReagentsAll reagents shall be of an analytical grade.5.1 Solvents, for the extraction according to ISO 1407.5.2 Inert carrier gas.6 Equipment6.1 Extraction de
28、vices according to ISO 1407.6.2 The chromatographic equipment consists of three associated parts:a) pyrolysis system;b) gas chromatograph equipped with chromatographic columns;c) mass detector in electronic impact mode.These elements are connected with an acquisition and data processing system.A sch
29、ematic diagram of the equipment is given in Annex A.6.2.1 Pyrolysis systemNon-volatile polymers are decomposed at elevated temperature to generate volatile products able to be analysed by chromatography. In order to obtain reproducible results of decomposition, the pyrolysis parameters (temperature,
30、 time) need to be established separately.Different types of equipment are available that give a rapid and reproducible pyrolysis. The three most common are: platinum filament pyrolyser; Curie point pyrolyser; micro furnace pyrolyser.6.2.2 Chromatographic columns6.2.2.1 GeneralThere are several categ
31、ories of chromatographic columns available in the market. They are characterized by: the nature of the material constituting the tube (generally silica covered with a polymer, aluminium or deactivated stainless steel, etc.); the column length; the column diameter; the nature, thickness, and polarity
32、 of the stationary phase placed on the internal surface of the capillary tube.The column shall be chosen by taking into account its efficiency of separation (number of theoretical plates) and the relative polarity of the various compounds generated during rubber pyrolysis. ISO 2013 All rights reserv
33、ed 3BS ISO 17257:2013ISO 17257:2013(E)6.2.2.2 Examples of useful capillary columnsa) Capillary column in fused silica of 0,32 mm diameter and 30 m , of apolar type. Stationary phase - film of dimethyl polysiloxane, 1 m thick;b) Capillary column in fused silica of 0,32 mm diameter and 30 m , of polar
34、 type. Stationary phase - film of polyethylene glycol, 0,5 m thick.7 Operating conditions7.1 GeneralThe reproducibility is guaranteed by checking the conformity of the device and by respecting the procedure.7.2 Gas chromatograph adjustmentAdjust the various controls of the gas chromatograph accordin
35、g to the retained operating conditions.For information, typical operating conditions are given in Annex B.7.3 ExtractionCarry out the extraction according to ISO 1407. The rubber residue is dried until constant mass.NOTE This preliminary extraction is not mandatory but allows the elimination of comp
36、ound constituents which could interfere with the pyrolysis product.7.4 Test portionTake a test portion of mass appropriate to the apparatus used, usually about 0,1 mg.7.5 PyrolysisPlace the test portion in the pyrolysis device and purge for the necessary time.Pyrolyse at a temperature between 400 C
37、and 800 C; usually the pyrolysis temperature is about 600 C.Record the experimental data.8 Interpretation of results8.1 GeneralThe identification of rubbers is achieved by noting the presence of certain characteristic decomposition products and by consulting the mass spectra database.Two examples of
38、 chromatograms are presented in Annex C.The following clauses summarize all the characteristic products by family of polymer. For the interpretation of the results, refer to Annex D according to the type of column used.8.2 Group M8.2.1 Chloropolyethylene (CM) and chlorosulfonylpolyethylene (CSM) Hyd
39、rochloric acid (CAS 7647-01-0)4 ISO 2013 All rights reservedBS ISO 17257:2013ISO 17257:2013(E) Benzene (CAS 71-43-2)It is possible, in certain case, to differentiate these two polymers by the presence of sulfur dioxide (CAS 7446-09-5).8.2.2 Ethylene-propylene copolymer (EPM) and Ethylene-propylene-d
40、iene terpolymer (EPDM) Propene (CAS 115-07-1) 1-Hexene (CAS 592-41-6) or 2-Methyl-1-pentene (CAS 763-29-1) 1-Heptene (CAS 592-76-7) or 5-Methyl-1-hexene (CAS 3524-73-0) 2-Methyl-1-heptene (CAS 15870-10-7) 1,3,5-Cycloheptatriene (CAS 544-25-2)8.2.3 Fluorocarbon rubber having substituent fluoro, perfl
41、uoroalkyl, or perfluoroalkoxy groups on the polymer chain (FKM) 1,1-Difluoroethene (CAS 75-38-7)8.3 Group O8.3.1 Homopolymer of epichlorhydrin (CO), copolymer of epichlorhydrin-ethylene oxide (ECO), terpolymer of epichlorhydrin-ethylene oxide-allyl glycidyl ether (GECO) Hydrochloric acid (CAS 7647-0
42、1-0) 1-Chloro-1-propene (CAS 590-21-6)8.4 Group Q8.4.1 Polysiloxanes (MQ, VMQ, PVMQ) Hexamethylcyclotrisiloxane (CAS 541-05-9) Octamethylcyclotetrasiloxane (CAS 556-67-2) Decamethylcyclopentasiloxane (CAS 541-02-6) Dodecamethylcyclohexasiloxane (CAS 540-97-6)The presence of benzene allows the polyme
43、rs PVMQ of the VMQ and MQ to be distinguished.8.5 Group R8.5.1 Butadiene rubber (BR) 1,3-Butadiene (CAS 106-99-0) 4-Ethenylcyclohexene or 4-Vinyl-1-cyclohexene (CAS 100-40-3)8.5.2 Chloroprene rubber (CR) Hydrochloric acid (CAS 7647-01-0) 2-Chloro-1,3-butadiene (CAS 126-99-8) 1-Chloro-5-(1-chloroethe
44、nyl)-cyclohexene (CAS 13547-07-4) ISO 2013 All rights reserved 5BS ISO 17257:2013ISO 17257:2013(E) 1-Chloro-4-(1-chloroethenyl)-cyclohexene (CAS 13547-06-3)8.5.3 Isobutene-isoprene rubber (IIR), chlorinated IIR (CIIR) and brominated IIR (BIIR) Isobutylene (CAS 115-11-7) Diisobutylene or 2,4,4-trimet
45、hyl-1-pentene (CAS 107-39-1) Triisobutylene or 2-methylpropane (CAS 7756-94-7)8.5.4 Natural rubber (NR) or synthetic isoprene rubber (IR) Isoprene (CAS 78-79-5)Isomers of the limonene: 1-Methyl-5-(1-methylethenyl)-cyclohexene (CAS 13898-73-2) 1-Methyl-4-(1-methylethenyl)-cyclohexene (CAS 138-86-3)8.
46、5.5 Acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (HNBR) and carboxylated NBR (XNBR)8.5.5.1 NBR and XNBR 1,3-Butadiene (CAS 106-99-0) 4-Ethenylcyclohexene or 4-Vinyl-1-cyclohexene (CAS 100-40-3) 2-Propenenitrile or Acrylonitrile (CAS 107-13-1)8.5.5.2 HNBR 2-Propenenitrile or Acrylonitrile (
47、CAS 107-13-1) Hexanenitrile or Capronitrile (CAS 628-73-9)8.5.6 Styrene-butadiene rubber (SBR) 1,3-Butadiene (CAS 106-99-0) 4-Ethenylcyclohexene or 4-Vinyl-1-cyclohexene (CAS 100-40-3) Ethenylbenzene or Styrene (CAS 100-42-5)In case of butadiene-alpha-methylstyrene copolymers, there is a strong peak
48、 of alpha-methylstyrene or isopropenylbenzene (CAS 98-83-9).9 Test reportThe test report shall include the following particulars:a) sample details: a full description of the sample;b) test method: a reference to this International Standard, (i.e. ISO 17257:2013); characteristics of the column, if ne
49、cessary thermal program and spectral condition; identification of the pyrolyser GC-MS equipment used;6 ISO 2013 All rights reservedBS ISO 17257:2013ISO 17257:2013(E)c) test details: details of any procedures not specified in this International Standard, if any;d) test results: chromatogram of sample; identification of the rubber(s) in the sample;e) date of test. ISO 2013 All rights reserved 7BS ISO 17257:2013ISO 17257:2013(E)Annex A (informative) Schematic diagram of the chro
