1、BSI Standards PublicationBS ISO 17257:2013Rubber Identification ofpolymers Pyrolytic gas-chromatographic method usingmass-spectrometric detectionCopyright British Standards Institution Provided by IHS under license with BSI - Uncontrolled Copy Not for ResaleNo reproduction or networking permitted wi
2、thout license from IHS-,-,-BS ISO 17257:2013 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 17257:2013.The UK participation in its preparation was entrusted to TechnicalCommittee PRI/23, Test methods for rubber and non-blackcompounding ingredients.A list of or
3、ganizations 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 responsible for its correctapplication. The British Standards Institution 2014. Published by BSI StandardsLimited 201
4、4ISBN 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 theStandards Policy and Strategy Committee on 28 February 2014.Amendments issued since publicationDate Text affectedCopyright Br
5、itish Standards Institution Provided by IHS under license with BSI - Uncontrolled Copy Not for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS ISO 17257:2013 ISO 2013Rubber Identification of polymers Pyrolytic gas-chromatographic method using mass-spectrometric detectio
6、nCaoutchouc Identification des polymres Mthode par pyrolyse et chromatographie en phase gazeuse avec dtection par spectromtrie de masseINTERNATIONAL STANDARDISO17257First edition2013-12-15Reference numberISO 17257:2013(E)Copyright British Standards Institution Provided by IHS under license with BSI
7、- Uncontrolled Copy Not for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS ISO 17257:2013ISO 17257:2013(E)ii ISO 2013 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2013All rights reserved. Unless otherwise specified, no part of this publication may be reproduced
8、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 ISOs member body in the country of the requester.ISO c
9、opyright officeCase postale 56 CH-1211 Geneva 20Tel. + 41 22 749 01 11Fax + 41 22 749 09 47E-mail copyrightiso.orgWeb www.iso.orgPublished in SwitzerlandCopyright British Standards Institution Provided by IHS under license with BSI - Uncontrolled Copy Not for ResaleNo reproduction or networking perm
10、itted without license from IHS-,-,-BS ISO 17257:2013ISO 17257:2013(E) ISO 2013 All rights reserved iiiContents PageForeword iv1 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 Ope
11、rating conditions . 47.1 General . 47.2 Gas chromatograph adjustment . 47.3 Extraction 47.4 Test portion 47.5 Pyrolysis 48 Interpretation 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
12、 equipment 8Annex B (informative) Examples of operating conditions . 9Annex C (informative) Chromatogram examples .10Annex D (informative) Chemical compounds identified in rubber pyrolysates .11Copyright British Standards Institution Provided by IHS under license with BSI - Uncontrolled Copy Not for
13、 ResaleNo reproduction or networking permitted without license from IHS-,-,-BS 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
14、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
15、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 in the ISO/IEC Directives, Part 1. In particular
16、 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 possibility that some of the elements of this do
17、cument 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 list of patent declarations received (see www.iso.
18、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 as information about ISOs adherence to the WTO
19、 principles 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 reservedCopyright British Standards Ins
20、titution Provided by IHS under license with BSI - Uncontrolled Copy Not for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS ISO 17257:2013INTERNATIONAL STANDARD ISO 17257:2013(E)Rubber Identification of polymers Pyrolytic gas-chromatographic method using mass-spectromet
21、ric detection1 ScopeThis International Standard provides a qualitative method for the identification of rubbers by their pyrolysis products using tandem the gas-chromatography /mass spectrometry.The method applies to rubbers in the raw state and to unvulcanized and vulcanized compounds. Compounds ca
22、n 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 of rubbers is given in Clause 3.2 Normative referencesThe following documents, in whole or in part, are norm
23、atively 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 1407, Rubber Determination of solvent extractISO 1629, Rub
24、ber 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 Chlorosulfonylpolyethylene (CSM)3.1.3 Ethylene-propylene copolymer (EPM) and Ethylene-propylene-diene terpolymer (EPDM)The meth
25、od 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 between them. ISO 2013 All rights reserved 1Copyright British Standards Institution Provided by IHS under license
26、with BSI - Uncontrolled Copy Not for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS 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 g
27、lycidyl ether (GECO)The method cannot distinguish between them.3.3 Group Q3.3.1 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 rubb
28、er (IIR), chlorinated IIR (CIIR) and brominated IIR (BIIR)The method cannot 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)T
29、he method can only distinguish HNBR from the two other polymers (NBR and XNBR).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/B
30、R, NBR/BR), the technique does not allow the homopolymer to be distinguished.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 chromatograph
31、y with mass spectrometric detection.4.2 The interpretation of the results is made by examining the mass spectra of the specific chromatographic peaks.2 ISO 2013 All rights reservedCopyright British Standards Institution Provided by IHS under license with BSI - Uncontrolled Copy Not for ResaleNo repr
32、oduction or networking permitted without license from IHS-,-,-BS 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 devices according to ISO 1407.6.2 The chromato
33、graphic 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 schematic diagram of the equipment is given in
34、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, time) need to be established separately.Dif
35、ferent 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 categories of chromatographic columns available i
36、n 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 of the stationary phase placed on the inter
37、nal 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 reserved 3Copyright British Standards Institution
38、Provided by IHS under license with BSI - Uncontrolled Copy Not for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS 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 typ
39、e. 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 type. Stationary phase - film of polyethylene glycol, 0,5 m thick.7 Operating conditions7.1 GeneralThe reproducibility is guaranteed by checking the conformity o
40、f the device and by respecting the procedure.7.2 Gas chromatograph adjustmentAdjust the various controls of the gas chromatograph according to the retained operating conditions.For information, typical operating conditions are given in Annex B.7.3 ExtractionCarry out the extraction according to ISO
41、1407. The rubber residue is dried until constant mass.NOTE This preliminary extraction is not mandatory but allows the elimination of compound 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,
42、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 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 ac
43、hieved by noting the presence of certain characteristic decomposition products and by consulting the mass spectra database.Two examples of chromatograms are presented in Annex C.The following clauses summarize all the characteristic products by family of polymer. For the interpretation of the result
44、s, refer to Annex D according to the type of column used.8.2 Group M8.2.1 Chloropolyethylene (CM) and chlorosulfonylpolyethylene (CSM) Hydrochloric acid (CAS 7647-01-0)4 ISO 2013 All rights reservedCopyright British Standards Institution Provided by IHS under license with BSI - Uncontrolled Copy Not
45、 for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS 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
46、Ethylene-propylene-diene 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 subst
47、ituent fluoro, perfluoroalkyl, 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) Hydrochlo
48、ric acid (CAS 7647-01-0) 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 polymers 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)
