BS ISO 21561-1-2015 Styrene-butadiene rubber (SBR) Determination of the microstructure of solution-polymerized SBR 1H-NMR and IR with cast-film method《苯乙烯-丁二烯橡胶 (SBR) 溶聚苯乙烯-丁二烯橡胶微观.pdf

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1、BSI Standards PublicationBS ISO 21561-1:2015Styrene-butadiene rubber (SBR) Determination of the microstructure of solution-polymerized SBRPart 1: 1H-NMR and IR with cast-film methodBS ISO 21561-1:2015 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 21561-1:2015

2、. Together with BS ISO 21561-2, it supersedes BS ISO 21561:2005+A1:2010 which will be withdrawn upon publication of BS ISO 21561-2.The UK participation in its preparation was entrusted to Technical Committee PRI/23, Test methods for rubber and non-black compounding ingredients.A list of organization

3、s represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2015.Published by BSI Standards Limited 2015ISBN 9

4、78 0 580 86835 1 ICS 83.060 Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 July 2015.Amendments/corrigenda issued since publicationDate T e x t a f f e c t e

5、 d ISO 2015Styrene-butadiene rubber (SBR) Determination of the microstructure of solution-polymerized SBR Part 1: 1H-NMR and IR with cast-film methodCaoutchouc styrne-butadine (SBR) Dtermination de la microstructure du SBR polymris en solution Partie 1: Mthode 1H-NMR et IR avec film moulINTERNATIONA

6、L STANDARDISO 21561-1First edition 2015-07-15Reference number ISO 21561-1:2015(E)BS ISO 21561-1:2015ISO 21561-1:2015(E)ii ISO 2015 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2015, Published in SwitzerlandAll rights reserved. Unless otherwise specified, no part of this publication may be rep

7、roduced 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 request

8、er.ISO copyright officeCh. de Blandonnet 8 CP 401CH-1214 Vernier, Geneva, SwitzerlandTel. +41 22 749 01 11Fax +41 22 749 09 47copyrightiso.orgwww.iso.orgBS ISO 21561-1:2015ISO 21561-1:2015(E)Foreword iv1 Scope . 12 Normative references 13 NMR method (absolute method) . 13.1 Principle 13.2 Reagents 2

9、3.3 Apparatus 23.4 Sampling . 23.5 Procedure 23.6 Determination of the microstructure 34 IR method (relative method) . 44.1 Principle 44.2 Reagents 44.3 Apparatus 44.4 Sampling . 54.5 Procedure 54.5.1 Preparation of sample solution . 54.5.2 Preparation of film coating . 54.5.3 Measurement of IR spec

10、trum . 54.6 Determination of microstructure 64.6.1 Measurement of absorbance corresponding to each microstructure component 64.6.2 Calculation . 74.7 Conversion of the IR method results to absolute results 85 Precision . 96 Test report . 9Annex A (informative) Procedure for sample-film preparation a

11、nd measurement of microstructure by FTIR spectrophotometry 10Annex B (informative) Precision 15Bibliography .17 ISO 2015 All rights reserved iiiContents PageBS ISO 21561-1:2015ISO 21561-1:2015(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national st

12、andards bodies (ISO member bodies). The 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 o

13、rganizations, 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 of electrotechnical standardization.The procedures used to develop this document and those intended for i

14、ts further maintenance are described 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/d

15、irectives).Attention is drawn to the 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

16、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 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 rela

17、ted to conformity assessment, as well 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 45, Rubber and rubber products, Subcommittee SC 2,

18、 Testing and analyses.This first edition of ISO 21561-1, together with ISO 21561-2, cancels and replaces ISO 21561:2005, which has been technically and nominally revised with the following changes: the descriptions of Ds were modified in 4.6.2; some terms and expressions were revised to be aligned w

19、ith those in the ISO 21561-2 to be (ATR method); it also incorporates the Amendment, ISO 21561:2005/Amd 1:2010.ISO 21561 consists of the following parts, under the general title Styrene-butadiene rubber (SBR): Part 1: 1H-NMR and IR with cast-film method Part 2: FTIR with ATR methodiv ISO 2015 All ri

20、ghts reservedBS ISO 21561-1:2015INTERNATIONAL STANDARD ISO 21561-1:2015(E)Styrene-butadiene rubber (SBR) Determination of the microstructure of solution-polymerized SBR Part 1: 1H-NMR and IR with cast-film methodWARNING Persons using this International Standard should be familiar with normal laborat

21、ory practice. This International Standard does not purport to address all the safety problems, if any, associated with its use. It is the responsibility of the user to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions.CAUTION Certain p

22、rocedures specified in this International Standard may involve the use or generation of substances, or the generation of waste, that could constitute a local environmental hazard. Reference should be made to appropriate documentation on safe handling and disposal after use.1 ScopeThis part of ISO 21

23、561 specifies procedures for the quantitative determination of the microstructure of the butadiene and the content of styrene in solution-polymerized SBR (S-SBR) by 1H-NMR spectrometry as an absolute method and by IR spectrometry as a relative method. The styrene content is expressed in mass % relat

24、ive to the whole polymer. The trans, cis and vinyl contents are expressed in mol % relative to the butadiene. These methods are applicable only for raw rubber.NOTE 1 IR spectrometry can also give absolute values of microstructure by calibration with S-SBRs of known absolute microstructure obtained b

25、y 1H-NMR spectrometry.NOTE 2 Only “vinyl”, “trans” and “cis” are used in this part of ISO 21561. However, the expression of vinyl, trans and cis mean as follows in general: vinyl: vinyl unit, vinyl bond, 1,2-unit, 1,2-bond, 1,2-vinyl-unit or 1,2-vinyl-bond; trans: 1,4-trans unit, 1,4-trans bond, tra

26、ns-1,4 unit or trans1,4 bond; cis: 1,4-cis unit, 1,4-cis bond, cis-1,4 unit or cis-1,4 bond.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.

27、 For undated references, the latest edition of the referenced document (including any amendments) applies.ISO 1407, Rubber Determination of solvent extractISO 1795, Rubber, raw natural and raw synthetic Sampling and further preparative procedures3 NMR method (absolute method)3.1 Principle3.1.1 A sma

28、ll quantity of an extracted S-SBR is dissolved in deuterated chloroform. ISO 2015 All rights reserved 1BS ISO 21561-1:2015ISO 21561-1:2015(E)3.1.2 A 1H-NMR spectrum of the sample solution is measured at a 15 ppm sweep width.With the peak areas obtained from 1H-NMR, calculate the microstructure of th

29、e butadiene portion and the styrene content by the theoretical formulae.3.2 Reagents3.2.1 Deuterated chloroform, CDCl3, containing 0,03 % of tetramethyl silane (TMS) as internal standard. The purity of the CDCl3itself shall be 99,8 %.3.2.2 Ethanol-toluene azeotrope (ETA).3.2.3 Acetone.3.3 Apparatus3

30、.3.1 1H-NMR spectrometer, Fourier transform nuclear magnetic resonance (FT-NMR) spectrometer with a resonance frequency of 150 MHz or higher.3.3.2 Extraction apparatus, as described in ISO 1407.3.3.3 Vacuum oven, operated at 50 C to 60 C.3.3.4 Analytical balance, accurate to 0,1 mg.3.4 SamplingThe r

31、aw rubber shall be sampled in accordance with ISO 1795.3.5 Procedure3.5.1 Extract rubber additives such as extender oil and antioxidants in accordance with ISO 1407, using ETA or acetone as the extraction solvent. Dry the extracted S-SBR under vacuum in the oven at 50 C to 60 C.3.5.2 Take 15 mg to 5

32、0 mg of the extracted S-SBR and dissolve it completely in 0,5 ml of deuterated chloroform (3.2.1). The concentration of this sample solution shall be selected according to the resolution of the spectrometer used.3.5.3 Measure the 1H-NMR spectrum of the S-SBR solution and a solvent blank deuterated c

33、hloroform (3.2.1) under the following conditions:Mode single-pulse modeMeasurement temperature room temperature to 50 CNo. of data points 32 kOffset 5 ppmSweep width 15 ppm or widerFlip angle 30 pulse2 ISO 2015 All rights reservedBS ISO 21561-1:2015ISO 21561-1:2015(E)Pulse repetition 4 s to 30 sAccu

34、mulation 32 times to 256 times3.6 Determination of the microstructure3.6.1 Integrate the signal intensities of the 1H-NMR spectrum over each of the areas A, B and C defined in Table 1. Figure 1 gives an example of a 1H-NMR spectrum showing the areas A, B and C.Table 1 Definition of signal integratio

35、n areasArea Signal integration rangeA From 4,3 ppm to minimum intensity point around 5,0 ppmBFrom minimum intensity point around 5,0 ppm to minimum intensity point around 6,1 ppmC From minimum intensity point around 6,1 ppm to 7,7 ppmTMSblankIntegrated signal intensity of TMS in CDCl3containing TMSC

36、DblankFrom 6,1 ppm to 7,7 ppm in CDCl3containing TMSTMS Integrated signal intensity of TMS in S-SBR sample solution100,00030,6587CX 8 6 4 2 010,8348BA0,9259KeyX shift (ppm)A, B, C signal integration areasFigure 1 Example of a Text 1H-NMR spectrum for an S-SBR3.6.2 Normalize the solvent blank measure

37、d in 3.5.3 using Formula (1) and subtract it from the signal intensity of the solvent determined from the integrated signal intensity of area C: ISO 2015 All rights reserved 3BS ISO 21561-1:2015ISO 21561-1:2015(E)CCCD TMSTMScalibblank blank/= ()(1)whereCcalibis the integrated signal intensity of are

38、a C compensated for the effect of CHCl3in CDCl3.3.6.3 Calculate the content of each microstructure component (trans and cis, and vinyl) of the butadiene portion and the styrene content, using Formulae (2) to (4):SCCBAm=(5) 104(5) 104 +( 2+ 4) 54100calibcalib (2)VABA=22+ 4100 (3)TCBABA=2- 42+ 4100 (4

39、)whereSmis the styrene content of the S-SBR, in mass %;V is the vinyl content of the butadiene portion of the S-SBR, in mol %;TC is the trans and the cis content of the butadiene portion of the S-SBR, in mol %.4 IR method (relative method)4.1 Principle4.1.1 A small quantity of extracted S-SBR is dis

40、solved in cyclohexane and coated on a KBr plate.4.1.2 The IR spectrum of the S-SBR sample on the KBr plate is measured over the range from 1 200 cm1to 600 cm1. From the absorbances at four specified wavelengths, the contents of the trans, the cis, the vinyl and the styrene are calculated using Hampt

41、ons method (see Reference 1 in the Bibliography).4.1.3 IR spectrometry can also give absolute values of microstructures by calibration with S-SBRs of known absolute microstructure obtained by 1H-NMR spectrometry.4.2 Reagents4.2.1 Ethanol-toluene azeotrope (ETA).4.2.2 Acetone.4.2.3 Cyclohexane.4.3 Ap

42、paratus4.3.1 IR spectrophotometer, Fourier transform infrared (FTIR) spectrophotometer or double-beam IR spectrophotometer.4 ISO 2015 All rights reservedBS ISO 21561-1:2015ISO 21561-1:2015(E)4.3.2 Extraction apparatus, as described in ISO 1407.4.3.3 Vacuum oven, operated at 50 C to 60 C.4.3.4 Analyt

43、ical balance, accurate to 0,1 mg.4.3.5 20 ml sample vial, with cap.4.3.6 Pasteur pipette, and 10 ml pipette.4.3.7 KBr plate, for IR spectrophotometry.4.3.8 Holder, for KBr plate.4.3.9 Metal spacer, of 0,1 mm thickness.4.4 SamplingThe raw rubber shall be sampled in accordance with ISO 1795.4.5 Proced

44、ure4.5.1 Preparation of sample solution4.5.1.1 Extract extender oil and antioxidant from the S-SBR in accordance with ISO 1407, using ETA or acetone. Dry the extracted S-SBR in a vacuum oven at 50 C to 60 C.4.5.1.2 Put 0,2 g of extracted S-SBR sample in a 20 ml sample vial.4.5.1.3 Add 10 ml of cyclo

45、hexane to the sample vial using the 10 ml pipette. Place the cap on the vial and shake to dissolve the S-SBR completely.4.5.2 Preparation of film coating4.5.2.1 Place the 0,1 mm thick metal spacer on the KBr plate and spread the sample solution uniformly in the spacer hole using the Pasteur pipette.

46、4.5.2.2 Remove any excess sample solution from the spacer, leaving a film of uniform thickness. As film thickness affects absorbance, adjust the volume of sample solution accordingly.4.5.2.3 Dry the sample solution on the KBr plate.4.5.2.4 Remove the spacer from the KBr plate and place the KBr plate

47、 in the holder ready for insertion in the IR spectrophotometer.NOTE Details of the equipment and procedure for preparing the film coating are given in Annex A.4.5.3 Measurement of IR spectrum4.5.3.1 Measurement by Fourier transform IR spectrophotometer4.5.3.1.1 Measure the background spectrum of a b

48、lank KBr plate from 1 200 cm1to 600 cm1. ISO 2015 All rights reserved 5BS ISO 21561-1:2015ISO 21561-1:2015(E)4.5.3.1.2 Measure the spectrum of the sample KBr plate from 1 200 cm1to 600 cm1.4.5.3.1.3 In order to ensure good reproducibility, the maximum absorbance for the sample spectrum shall be in t

49、he range from 0,10 to 0,15.4.5.3.1.4 An example of an FTIR spectrum is shown in Figure 2.4.5.3.2 Measurement by double-beam IR spectrophotometer4.5.3.2.1 Place blank KBr plates in both the sample and reference paths, and measure the background spectrum from 1 200 cm1to 600 cm1in the absorbance mode.4.5.3.2.2 Place the sample KBr plate in the sample path and a blank KBr plate in the reference path. Measure the sample spectrum from 1 200 cm1to 600 cm1in the absorbance mode.4.5.3.2.3 In ord