BS ISO 21561-2-2016 Styrene-butadiene rubber (SBR) Determination of the microstructure of solution-polymerized SBR FTIR with ATR method《苯乙烯-丁二烯橡胶 (SBR) 溶聚苯乙烯-丁二烯橡胶微观结构的测定 ATR法的FTIR.pdf

1、BSI Standards PublicationBS ISO 21561-2:2016Styrene-butadiene rubber(SBR) Determination of themicrostructure of solution-polymerized SBRPart 2: FTIR with ATR methodBS ISO 21561-2:2016 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 21561-2:2016. Together with B

2、S ISO 21561-1:2015, it supersedes BS ISO 21561:2005+A1:2010 which is withdrawn.The UK participation in its preparation was entrusted to Technical Committee PRI/22, Testing and analysis of rubber.A list of organizations represented on this committee can be obtained on request to its secretary.This pu

3、blication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2016.Published by BSI Standards Limited 2016ISBN 978 0 580 84718 9 ICS 83.060 Compliance with a British Standard cannot confer immuni

4、ty from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 March 2016.Amendments/corrigenda issued since publicationDate T e x t a f f e c t e dBS ISO 21561-2:2016 ISO 2016Styrene-butadiene rubber (SBR) Determination of the

5、microstructure of solution-polymerized SBR Part 2: FTIR with ATR methodCaoutchouc styrne-butadine (SBR) Dtermination de la microstructure du SBR polymris en solution Partie 2: Mthode FTIR avec ATRINTERNATIONAL STANDARDISO21561-2First edition2016-03-01Reference numberISO 21561-2:2016(E)BS ISO 21561-2

6、:2016ISO 21561-2:2016(E)ii ISO 2016 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2016, Published in SwitzerlandAll rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including

7、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 copyright officeCh. de Blandonnet 8 CP 401CH-1214 Vernier, Geneva, SwitzerlandTel. +41 2

8、2 749 01 11Fax +41 22 749 09 47copyrightiso.orgwww.iso.orgBS ISO 21561-2:2016ISO 21561-2:2016(E)Foreword iv1 Scope . 12 Normative references 13 Principle 14 Apparatus . 25 Calibration 25.1 FTIR 25.2 ATR 26 Sampling 27 Procedure for measuring ATR spectrum . 28 Determination of the microstructure of b

9、utadiene and the styrene content . 38.1 Measurement of the absorbance for each microstructure component 38.2 Calculation of microstructures 48.2.1 General 48.2.2 Base line correction of each absorbance peak . 58.2.3 Ratio of absorbance . 58.2.4 Second order terms . 58.2.5 Styrene content and microst

10、ructures in mass % by regression formulae . 58.2.6 Microstructures in mol % 69 Precision . 610 Test report . 6Annex A (informative) Precision results from an interlaboratory test programme . 8Annex B (informative) Acquisition of regression formulae for microstructure 10Annex C (informative) Determin

11、ation of microstructure by NMR spectrometry .12Bibliography .16 ISO 2016 All rights reserved iiiContents PageBS ISO 21561-2:2016ISO 21561-2:2016(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of

12、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,

13、 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 in the ISO/

14、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 possibility

15、 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 list of paten

16、t 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 as informa

17、tion 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, Testing and analysis.This first edition of ISO

18、21561-2 cancels and replaces ISO 21561:2005, which has been technically revised. It also incorporates Amendment ISO 21561:2005/Amd.1:2010.ISO 21561 consists of the following parts, under the general title Styrene-butadiene rubber (SBR) Determination of the microstructure of solution-polymerized SBR:

19、 Part 1: 1H-NMR and IR with cast-film method Part 2: FTIR with ATR methodiv ISO 2016 All rights reservedBS ISO 21561-2:2016INTERNATIONAL STANDARD ISO 21561-2:2016(E)Styrene-butadiene rubber (SBR) Determination of the microstructure of solution-polymerized SBR Part 2: FTIR with ATR methodWARNING Pers

20、ons using this part of ISO 21561 should be familiar with normal laboratory practice. This part of ISO 21561 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 co

21、mpliance with any national regulatory conditions.CAUTION Certain procedures specified in this part of ISO 21561 might 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

22、safe handling and disposal after use.1 ScopeThis part of ISO 21561 specifies procedures for the quantitative determination of the microstructure of the butadiene and the content of styrene in solution-polymerized SBR (S-SBR) by Fourier Transform Infrared Spectrometry (FTIR) with Attenuated Total Ref

23、lection (ATR) method. The styrene content is expressed in mass % relative to the whole polymer. The vinyl, trans and cis contents are expressed in mol % relative to the butadiene content. This method is only applicable to raw rubbers.NOTE 1 Precision as shown in Annex A may not be obtained for S-SBR

24、s containing polystyrene block or styrene content more than 45 mass %.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

25、-bond; trans: 1,4-trans unit, 1,4-trans bond, trans-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

26、dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.ISO 1795, Rubber, raw natural and raw synthetic Sampling and further preparative procedures3 PrincipleThe IR spectrum of the S-SBR sample is meas

27、ured by FTIR with ATR. The absorbances that are characteristic of each microstructure component and styrene at the specified wavelengths are used to determine the content of each component by using the specific formulae presented in this part of ISO 21561. ISO 2016 All rights reserved 1BS ISO 21561-

28、2:2016ISO 21561-2:2016(E)4 Apparatus4.1 FTIR, of the following specifications: Detector: Deuterium Tri-Glycine Sulfate (DTGS) or Tri-Glycine Sulfate (TGS); Number of scans: 32; Resolution: 2 cm1; Range of wavelength: 600 cm1to 1 800 cm1.4.2 ATR, of the following specifications: Type: Single bounce A

29、TR; Crystal: Diamond; Angle of incidence: 45; Sample pressure clamp: A concave or a flat-shaped clamp which is capable of maintaining a constant pressure on the sample. The use of a torque wrench is preferable.5 Calibration5.1 FTIRAdjust the optical bench alignment of FTIR spectrometer according to

30、the manufacturers instruction manual.5.2 ATRSet ATR in the sample chamber of FTIR and adjust the optical alignment of ATR according to the manufacturers instruction manual.6 Sampling6.1 Prepare the test sample in accordance with ISO 1795.NOTE The extraction of ordinary extender oils by solvent is no

31、t necessary.6.2 Cut out a test piece from the test sample. The test piece shall have a flat surface to give good contact with the ATR crystal and be approximately the same size as the crystal, usually a few square millimetres.7 Procedure for measuring ATR spectrum7.1 Set up FTIR according to the man

32、ufacturers instruction manual.7.2 Set ATR in a sample chamber of FTIR.7.3 Measure the background spectrum with the conditions shown in 4.1.7.4 Put the test piece on the ATR crystal and contact it as completely as possible to the crystal surface, preferably using the clamp specified in 4.2. The conta

33、ct between the test piece and the crystal affects the absorbance of ATR spectra.2 ISO 2016 All rights reservedBS ISO 21561-2:2016ISO 21561-2:2016(E)7.5 Measure the sample spectrum with the conditions shown in 4.1.7.6 The atmosphere of the sample chamber for FTIR shall be kept consistent during the b

34、ackground and test piece measurements in order to avoid the influences of absorbance at 668 cm1and 723 cm1by CO2.8 Determination of the microstructure of butadiene and the styrene content8.1 Measurement of the absorbance for each microstructure componentMeasure the absorbance values at the wave numb

35、ers corresponding to the microstructure components as specified in Table 1. For cis, the absorption peaks are weak and the wave number of the peaks is affected by the styrene content of the polymer.Table 1 Measurement of absorbances for each microstructure component of S-SBRNotation for absorbanceMi

36、crostructure componentRemarksA10 Styrene Measure the absorbance at the peak maximum from 695 cm1to 700 cm1.A20 CisThe wave number at this peak maximum is affected by the nature of the polymer, such as the styrene content. When the peak maximum is visible, read off the absorbance at the peak maximum

37、from 720 cm1to 730 cm1.If the styrene content is over 30 %, the peak of the cis bond is hidden between the two large styrene absorptions at around 758 cm1and around 698 cm1. In this case, measure the absorbance value at 726 cm1.A30 Styrene Measure the absorbance at the peak maximum from 755 cm1to 76

38、1 cm1.A40 Vinyl Measure the absorbance at the peak maximum from 905 cm1to 912 cm1.A50 Trans Measure the absorbance at the peak maximum from 962 cm1to 967 cm1.A60 Vinyl Measure the absorbance at the peak maximum from 991 cm1to 996 cm1.A70 Base line Measure the absorbance at 1 200 cm1as zero point of

39、each absorbance. ISO 2016 All rights reserved 3BS ISO 21561-2:2016ISO 21561-2:2016(E)KeyX wave number (cm1)Y absorbanceFigure 1 ATR spectrum of a typical S-SBR8.2 Calculation of microstructures8.2.1 GeneralThe microstructure of S-SBR is calculated by using regression formulae and the measured absorb

40、ance values of the ATR spectra of each sample. The regression formulae were derived from a statistical study on the ATR spectra of various S-SBR samples with known microstructures. After adjusting the baseline of the ATR spectra, the absorbance ratio values of respective absorptions are obtained as

41、the parameter value for microstructure calculation. The microstructure results are calculated by substituting these parameter values in the regression formulae.4 ISO 2016 All rights reservedBS ISO 21561-2:2016ISO 21561-2:2016(E)8.2.2 Base line correction of each absorbance peakObtain the absorbance

42、of each of the peaks A11 to A61 with corrected base lines by using Formulae (1) to (6):A11 = A10 A70 (1)A21 = A20 A70 (2)A31 = A30 A70 (3)A41 = A40 A70 (4)A51 = A50 A70 (5)A61 = A60 A70 (6)8.2.3 Ratio of absorbanceObtain the ratios of the absorbances A12 to A62 by using Formulae (7) to (12):A12 = (A

43、11)/(A11 + A21 + A31 + A41 + A51 + A61) (7)A22 = (A21)/(A11 + A21 + A31 + A41 + A51 + A61) (8)A32 = (A31)/(A11 + A21 + A31 + A41 + A51 + A61) (9)A42 = (A41)/(A11 + A21 + A31 + A41 + A51 + A61) (10)A52 = (A51)/(A11 + A21 + A31 + A41 + A51 + A61) (11)A62 = (A61)/(A11 + A21 + A31 + A41 + A51 + A61) (12

44、)8.2.4 Second order termsCalculate the second order terms which are the squares of A12 to A62.8.2.5 Styrene content and microstructures in mass % by regression formulaeThe content (mass %) of each microstructure component is expressed by the following regression Formulae (13) to (16):Sm= 9,0 + 12,9

45、(A12) + 25,9 (A12)2 111,2 (A22) + 412,5 (A22)2+ 105,0 (A32) + 891,9 (A32)2 0,5 (A42) 21,5 (A42)2 30,7 (A52) + 28,9 (A52)2+ 24,5 (A62) 47,2 (A62)2(13) ISO 2016 All rights reserved 5BS ISO 21561-2:2016ISO 21561-2:2016(E)Vm= 32,9 + 5,3 (A12) 12,9 (A12)2 183,6 (A22) + 1 168,4 (A22)2+ 13,2 (A32) 572,5 (A

46、32)2+ 33,7 (A42) + 3,5 (A42)2 90,5 (A52) + 33,5 (A52)2+ 129,6 (A62) + 168,9 (A62)2(14)Tm= 42,5 16,3 (A12) 18,8 (A12)2+ 61,4 (A22) 1 368,2 (A22)2 65,1 (A32) 127,7 (A32)2 19,6 (A42) + 14,9 (A42)2+ 93,3 (A52) 13,9 (A52)2 129,8 (A62) 116,6 (A62)2(15)Cm= 15,6 1,9 (A12) + 5,8 (A12)2+ 233,5 (A22) 212,6 (A2

47、2)2 53,1 (A32) 191,7 (A32)2 13,6 (A42) + 3,1 (A42)2+ 27,9 (A52) 48,5 (A52)2 24,3 (A62) 5,1 (A62)2(16)whereSmis the styrene content of the S-SBR, in mass %;Vmis the vinyl content of the S-SBR, in mass %;Tmis the trans content of the S-SBR, in mass %;Cmis the cis content of the S- SBR, in mass %.8.2.6

48、 Microstructures in mol %The content (mol %) in butadiene is expressed by Formulae (17) to (19):V = Vm/(Vm+ Tm+ Cm) 100 (17)T = Tm/(Vm+ Tm+ Cm) 100 (18)C = Cm/(Vm+ Tm+ Cm) 100 (19)whereV is the vinyl content of the butadiene portion of the S-SBR, in mol %;T is the trans content of the butadiene port

49、ion of the S-SBR, in mol %;C is the cis content of the butadiene portion of the S-SBR, in mol %.9 PrecisionSee Annex A.10 Test reportThe test report shall include at least the following information:a) sample details:1) a full description of the sample and its origin;2) if appropriate, method of preparation of test piece from the sample;b)