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1、BRITISH STANDARD BS ISO 21561:2005 Styrene-butadiene rubber (SBR) Determination of the microstructure of solution-polymerized SBR ICS 83.060 ? Licensed Copy: sheffieldun sheffieldun, na, Mon Nov 27 07:49:52 GMT+00:00 2006, Uncontrolled Copy, (c) BSI BS ISO 21561:2005 This British Standard was publis
2、hed under the authority of the Standards Policy and Strategy Committee on 4 January 2006 BSI 4 January 2006 ISBN 0 580 47395 3 National foreword This British Standard reproduces verbatim ISO 21561:2005 and implements it as the UK national standard. The UK participation in its preparation was entrust
3、ed to Technical Committee PRI/23, Test methods for rubber and non-black compounding ingredients, which has the responsibility to: aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep U
4、K interests informed; monitor related international and European developments and promulgate them in the UK. A list of organizations represented on this committee can be obtained on request to its secretary. Cross-references The British Standards which implement international publications referred t
5、o in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. This publication does not purport to include all the necessary provisions
6、of a contract. Users are responsible for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. Summary of pages This document comprises a front cover, an inside front cover, the ISO title page, pages ii to iv, pages 1 to 15 and a back
7、cover. The BSI copyright notice displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. DateComments Licensed Copy: sheffieldun sheffieldun, na, Mon Nov 27 07:49:52 GMT+00:00 2006, Uncontrolled Copy, (c) BSI Reference number ISO 21561:2005
8、(E) INTERNATIONAL STANDARD ISO 21561 First edition 2005-12-01 Styrene-butadiene rubber (SBR) Determination of the microstructure of solution-polymerized SBR Caoutchouc styrne-butadine (SBR) Dtermination de la microstructure du SBR polymris en solution BS ISO 21561:2005 Licensed Copy: sheffieldun she
9、ffieldun, na, Mon Nov 27 07:49:52 GMT+00:00 2006, Uncontrolled Copy, (c) BSI ii Licensed Copy: sheffieldun sheffieldun, na, Mon Nov 27 07:49:52 GMT+00:00 2006, Uncontrolled Copy, (c) BSI BS ISO 21561:2005 iii Contents Page Foreword iv 1 Scope . 1 2 Normative references . 1 3 NMR method (absolute met
10、hod) . 1 4 IR method (relative method) 4 5 Precision 10 6 Test report . 11 Annex A (informative) Procedure for sample-film preparation and measurement of microstructure by FT IR spectrophotometry 12 Bibliography . 15 Licensed Copy: sheffieldun sheffieldun, na, Mon Nov 27 07:49:52 GMT+00:00 2006, Unc
11、ontrolled Copy, (c) BSI BS ISO 21561:2005 iv Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each memb
12、er 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 Ele
13、ctrotechnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adop
14、ted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. Attention is drawn to the possibility that some of the elements of this document may be the subject of pate
15、nt rights. ISO shall not be held responsible for identifying any or all such patent rights. ISO 21561 was prepared by Technical Committee ISO/TC 45, Rubber and rubber products, Subcommittee SC 2, Testing and analysis. Licensed Copy: sheffieldun sheffieldun, na, Mon Nov 27 07:49:52 GMT+00:00 2006, Un
16、controlled Copy, (c) BSI 1 Styrene-butadiene rubber (SBR) Determination of the microstructure of solution-polymerized SBR WARNING Persons using this International Standard should be familiar with normal laboratory practice. This standard does not purport to address all the safety problems, if any, a
17、ssociated 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. 1 Scope This International Standard specifies procedures for the quantitative determination of the microstructure of the
18、 butadiene units and the content of styrene units 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 % relative to the whole polymer. The 1,4-trans, 1,4-cis and 1,2-vinyl contents are
19、expressed in mol % relative to the butadiene units. NOTE IR spectrometry can also give absolute values of microstructure by calibration with S-SBRs of known absolute microstructure obtained by 1H-NMR spectrometry. 2 Normative references The following referenced documents are indispensable for the ap
20、plication of this document. 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 extract ISO 1795, Rubber, raw natural and raw synthetic Sampling and f
21、urther preparative procedures 3 NMR method (absolute method) 3.1 Principle 3.1.1 A small quantity of an extracted S-SBR is dissolved in deuterated-chloroform. 3.1.2 A 1H-NMR spectrum of the sample solution is measured at a 15 ppm sweep width. The peak areas of the 1,4-bond (the sum of the 1,4-trans
22、bond and 1,4-cis bond) and the 1,2-vinyl bond of the butadiene portion are determined along with the peak area of styrene. The microstructure of the butadiene portion and the styrene content are then calculated using theoretical formulae. 3.2 Reagents 3.2.1 Deuterated chloroform, CDCl3, containing 0
23、,03 % of tetramethyl silane (TMS) as internal standard. The purity of the CDCl3 itself shall be 99,8 %. 3.2.2 Anhydrous ethanol-toluene azeotrope (ETA). BS ISO 21561:2005 Licensed Copy: sheffieldun sheffieldun, na, Mon Nov 27 07:49:52 GMT+00:00 2006, Uncontrolled Copy, (c) BSI 2 3.2.3 Acetone. 3.3 A
24、pparatus 3.3.1 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
25、 Sampling The raw rubber shall be sampled in accordance with ISO 1795. 3.5 Procedure 3.5.1 Extract rubber additives such as extender oil and antioxidant in accordance with ISO 1407, using anhydrous ETA or acetone as the extraction solvent. Dry the extracted S-SBR under vacuum in the oven at 50 C to
26、60 C. 3.5.2 Take 15 mg to 50 mg of the extracted S-SBR and dissolve it completely in 0,5 ml of deuterated chloroform containing 0,03 % of TMS. The concentration of this sample solution shall be selected according to the resolution of the spectrometer used. 3.5.3 Transfer 0,5 ml of the S-SBR sample s
27、olution into an NMR tube for measurement. 3.5.4 Measure the 1H-NMR spectrum of the S-SBR solution under the following conditions: Mode single-pulse mode Measurement temperature room temperature to 50 C No. of data points 32 k Offset 5 ppm Sweep width 15 ppm or wider Flip angle 30 pulse Pulse repetit
28、ion 4 s to 30 s Accumulation 32 times to 256 times 3.6 Determination of the microstructure 3.6.1 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. BS ISO 21561:200
29、5 Licensed Copy: sheffieldun sheffieldun, na, Mon Nov 27 07:49:52 GMT+00:00 2006, Uncontrolled Copy, (c) BSI 3 Table 1 Definition of signal integration areas Area Signal integration range A From 4,3 ppm to minimum intensity point around 5,0 ppm B From minimum intensity point around 5,0 ppm to minimu
30、m intensity point around 6,1 ppm C From minimum intensity point around 6,1 ppm to 7,7 ppm TMSblank Integrated signal intensity of TMS in CDCl3 containing TMS CDblank From 6,1 ppm to 7,7 ppm in CDCl3 containing TMS TMS Integrated signal intensity of TMS in S-SBR sample solution Key X shift (ppm) A, B
31、, C signal integration areas Figure 1 Example of a 1H-NMR spectrum for an S-SBR 3.6.2 Measure as a solvent blank the 1H-NMR spectrum of the deuterated chloroform containing 0,03 % of TMS. The TMS blank is normalized using Equation (1) and subtracted from the signal intensity of the solvent determine
32、d from the integrated signal intensity of area C: () calibblankblank CCCDTMS/TMS= (1) BS ISO 21561:2005 Licensed Copy: sheffieldun sheffieldun, na, Mon Nov 27 07:49:52 GMT+00:00 2006, Uncontrolled Copy, (c) BSI 4 3.6.3 Calculate the content of each microstructure component (1,4-bond and 1,2-vinyl bo
33、nd) of the butadiene portion and the styrene content, using Equations (2) to (4): () ()() calib calib C/5104 % St100 C/5104B/2 A/454 = + (2) 1,2 A/2 % Bd100 B/2A/4 = + (3) 1,4 B/2 A/4 % Bd100 B/2A/4 = + (4) where Ccalib is the integrated signal intensity of area C compensated for the effect of CHCl3
34、 in CDCl3; % St is the styrene content of the SBR, in mass %; % Bd1,2 is the 1,2-vinyl bond content of the butadiene portion of the SBR, in mol %; % Bd1,4 is the 1,4-bond content of the butadiene portion of the SBR, in mol %. 4 IR method (relative method) 4.1 Principle 4.1.1 A small quantity of extr
35、acted S-SBR is dissolved 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 1 200 cm1 to 600 cm1. From the absorbances at four specified wavelengths, the contents of the 1,4-trans bond, the 1,4-cis bond, the 1,2-vinyl bond
36、and the styrene unit are calculated using Hamptons 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 Reagents 4.2.1 Anhydrous ethanol-to
37、luene azeotrope (ETA). 4.2.2 Acetone. 4.2.3 Cyclohexane. 4.3 Apparatus 4.3.1 IR spectrophotometer: Fourier transform infrared (FT-IR) spectrophotometer or double-beam IR spectrophotometer. 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
38、ical balance, accurate to 0,1 mg. BS ISO 21561:2005 Licensed Copy: sheffieldun sheffieldun, na, Mon Nov 27 07:49:52 GMT+00:00 2006, Uncontrolled Copy, (c) BSI 5 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 KB
39、r plate. 4.3.9 Metal spacer, of 0,1 mm thickness. 4.4 Sampling The raw rubber shall be sampled in accordance with ISO 1795. 4.5 Procedure 4.5.1 Preparation of sample solution 4.5.1.1 Extract extender oil and antioxidant from the S-SBR in accordance with ISO 1407, using anhydrous ETA or acetone. Dry
40、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 cyclohexane 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 coati
41、ng 4.5.2.1 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. 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 volu
42、me 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 in the holder ready for insertion in the IR spectrophotometer. NOTE Details of the equipment and procedure for preparing the film coating are give
43、n in Annex A. 4.5.3 Measurement of IR spectrum 4.5.3.1 Measurement by Fourier transform IR spectrophotometer 4.5.3.1.1 Measure the background spectrum of a blank KBr plate from 1 200 cm1 to 600 cm1. 4.5.3.1.2 Measure the spectrum of the sample KBr plate from 1 200 cm1 to 600 cm1. 4.5.3.1.3 In order
44、to ensure good reproducibility, the maximum absorbance for the sample spectrum shall be in the range 0,10 to 0,15. 4.5.3.1.4 An example of an FT-IR spectrum is shown in Figure 2. 4.5.3.2 Measurement by double-beam IR spectrophotometer BS ISO 21561:2005 Licensed Copy: sheffieldun sheffieldun, na, Mon
45、 Nov 27 07:49:52 GMT+00:00 2006, Uncontrolled Copy, (c) BSI 6 4.5.3.2.1 Place blank KBr plates in both the sample and reference paths, and measure the background spectrum from 1 200 cm1 to 600 cm1 in the absorbance mode. 4.5.3.2.2 Place the sample KBr plate in the sample path and a blank KBr plate i
46、n the reference path. Measure the sample spectrum from 1 200 cm1 to 600 cm1 in the absorbance mode. 4.5.3.2.3 In order to ensure good reproducibility, the maximum absorbance for the sample spectrum shall be in the range 0,10 to 0,15. 4.5.3.2.4 Produce a difference spectrum for the calculation of the
47、 microstructure by subtracting the background spectrum from the sample spectrum. Key 1 1,4-trans 2 1,2-vinyl 3 1,4-cis 4 styrene Figure 2 An example of an FT-IR spectrum for an S-SBR 4.6 Determination of microstructure 4.6.1 Measurement of absorbance corresponding to each microstructure component Me
48、asure the absorbance values at the wave numbers corresponding to the microstructure components as specified in Table 2. For “1,4-cis”, the absorption peak is weak and the wave number of the peak is affected by the styrene content of the polymer. BS ISO 21561:2005 Licensed Copy: sheffieldun sheffield
49、un, na, Mon Nov 27 07:49:52 GMT+00:00 2006, Uncontrolled Copy, (c) BSI 7 Table 2 Measurement of absorbances for each microstructure component of S-SBR Wave number Notation for absorbance Microstructure component cm1 Remarks Dtrans 1,4-trans bond 967 Measure the absorbance at the peak maximum. Dvinyl 1,2-vinyl bond 911 Measure the absorbance at the peak maximum. Dcis 1,4-cis bond 724 The wave number at this peak maximum is affected by the nature