1、BS ISO11089:2010ICS 83.040.10NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDRubber, raw synthetic Determination ofantidegradants byhigh-performanceliquid chromatographyThis British Standardwas published under theauthority of the StandardsPolicy and StrategyComm
2、ittee on 30 June2010 BSI 2010ISBN 978 0 580 65486 2Amendments/corrigenda issued since publicationDate CommentsBS ISO 11089:2010National forewordThis British Standard is the UK implementation of ISO 11089:2010. Itsupersedes BS 7164-31.1:1997 which is withdrawn.The UK participation in its preparation
3、was entrusted to TechnicalCommittee PRI/23, Test methods for rubber and non-black compoundingingredients.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisionsof a contract. Users are
4、responsible for its correct application.Compliance with a British Standard cannot confer immunityfrom legal obligations.BS ISO 11089:2010Reference numberISO 11089:2010(E)ISO 2010INTERNATIONAL STANDARD ISO11089Second edition2010-06-01Rubber, raw synthetic Determination of antidegradants by high-perfo
5、rmance liquid chromatography Caoutchouc synthtique brut Dtermination des agents de protection par chromatographie en phase liquide haute performance BS ISO 11089:2010ISO 11089:2010(E) PDF disclaimer This PDF file may contain embedded typefaces. In accordance with Adobes licensing policy, this file m
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8、he file is suitable for use by ISO member bodies. In the unlikely event that a problem relating to it is found, please inform the Central Secretariat at the address given below. COPYRIGHT PROTECTED DOCUMENT ISO 2010 All rights reserved. Unless otherwise specified, no part of this publication may be
9、reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or ISOs member body in the country of the requester. ISO copyright office Case postale 56 CH-1211 Geneva 20 Tel. + 41
10、 22 749 01 11 Fax + 41 22 749 09 47 E-mail copyrightiso.org Web www.iso.org Published in Switzerland ii ISO 2010 All rights reservedBS ISO 11089:2010ISO 11089:2010(E) ISO 2010 All rights reserved iiiContents Page Foreword iv 1 Scope1 2 Principle1 3 Materials .1 4 Apparatus.2 5 Chromatographic condit
11、ions .2 6 Procedure.3 7 Expression of results3 8 Precision.3 9 Test report4 Annex A (informative) Precision5 BS ISO 11089:2010ISO 11089:2010(E) iv ISO 2010 All rights reservedForeword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO
12、 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 organizations, gover
13、nmental 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. International Standards are drafted in accordance with the rules given in the ISO/IEC D
14、irectives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adopted 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
15、bodies casting a vote. 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. ISO 11089 was prepared by Technical Committee ISO/TC 45, Rubber and rubber pro
16、ducts, Subcommittee SC 2, Testing and analysis. This second edition cancels and replaces the first edition (ISO 11089:1997), which has been technically revised (N-phenyl-naphthylamine has been deleted from the antidegradants determined and precision data have been added as Annex A). BS ISO 11089:201
17、0INTERNATIONAL STANDARD ISO 11089:2010(E) ISO 2010 All rights reserved 1Rubber, raw synthetic Determination of antidegradants by high-performance liquid chromatography WARNING Persons using this International Standard should be familiar with normal laboratory practice. This standard does not purport
18、 to address all of 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 procedures specified in this International Standard may
19、 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 Scope This International Standard describes a procedure for the determination
20、 of the following antidegradants in raw synthetic rubbers: N-alkyl-N-phenyl-p-phenylenediamine; N-aryl-N-aryl-p-phenylenediamine; poly-2,2,4-trimethyl-1,2-dihydroquinoline. Extender oils, when present, can interfere. The method, with modification if necessary, can be applied to the determination of
21、other amine antidegradants. 2 Principle The antidegradant, following quantitative extraction from the rubber, is separated by high-performance liquid chromatography (HPLC) from other extracted components, and its component peaks detected and their areas measured. Its concentration in the rubber is c
22、alculated by comparison with the area of the antidegradant component peaks of a known amount of the same antidegradant analysed under the same analysis conditions. NOTE Some antidegradants contain more than one component peak and the ratio of the areas of single component peaks may differ depending
23、on the source of the antidegradant. The procedure described will give accurate results providing the composition of the reference antidegradant and the antidegradant being analysed contain the same number of component peaks with the same area ratios. Inaccurate results are obtained when this conditi
24、on is not satisfied, with the extent of the error being dependent on the difference in composition between reference and sample antidegradants. 3 Materials 3.1 Eluent A: a 1:1 (by volume) mixture of methanol (HPLC grade) and a 0,01 M aqueous solution of ammonium acetate (AR grade). 3.2 Eluent B: met
25、hanol (HPLC grade). BS ISO 11089:2010ISO 11089:2010(E) 2 ISO 2010 All rights reserved3.3 Extraction solvent: a 2:1 (by volume) mixture of isopropanol (HPLC grade) and dichloromethane (HPLC grade). 4 Apparatus 4.1 HPLC apparatus, with gradient elution capability, a 10 mm3fixed-loop injector, a variab
26、le-wavelength ultraviolet-visible (UV-VIS) detector and a recording-integrator data system. 4.2 HPLC column, reverse-phase type. Different columns may be used provided a good separation of antidegradant component peaks from other extracted components is obtained. The method has been tested using 5 m
27、 particle size HYPERSIL ODS and SPHERI-5 ODS1)columns. However, the elution programme might need to be modified when columns different from the ones described in this International Standard are used. 4.3 Ultrasonic bath, typically of about 2 dm3capacity, operating at a frequency of 47,6 kHz 10 %. An
28、 ultrasonic bath of different capacity and operating frequency may be used provided that extraction of the antidegradant is complete. 4.4 Analytical balance, capable of weighing to 0,01 mg. 5 Chromatographic conditions 5.1 Pump A: Elution solvent A (3.1). 5.2 Pump B: Elution solvent B (3.2). 5.3 Flo
29、w rate: 0,25 cm3/min. 5.4 Column oven temperature: 40 C. 5.5 Injection volume: 10 mm3(10 l). 5.6 Detector wavelength: poly-2,2,4-trimethyl-1,2-dihydroquinoline: 233 nm; all other antidegradants: 295 nm. 5.7 Reference wavelength: 550 nm. 5.8 Elution programme: Time Eluent A Eluent B min % % 0 100 0 2
30、0 0 100 40 0 100 50 100 0 55 End 1) HYPERSIL ODS and SPHERI-5 ODS are examples of suitable products available commercially. This information is given for the convenience of users of this document and does not constitute an endorsement by ISO of these products. BS ISO 11089:2010ISO 11089:2010(E) ISO
31、2010 All rights reserved 36 Procedure 6.1 On a laboratory mill, thinly sheet, to about 0,25 mm to 0,5 mm thickness, a representative sample of the rubber to be analysed. Cut about 1 g of the thinly sheeted sample into small pieces about 5 mm square. Carry out the procedure in 6.2 to 6.10 twice, on d
32、uplicate test portions. 6.2 Weigh, to the nearest 0,1 mg, about 200 mg of the small pieces and place each test portion into a 20 cm3flask. 6.3 Add accurately, by pipette, 10 cm3of extraction solvent (3.3) and stopper the flask. 6.4 Extract in the ultrasonic bath (4.3) for 3 h at a temperature not ex
33、ceeding 30 C. NOTE Should the bath temperature exceed 30 C, the flask could rupture. Therefore it might be necessary periodically to add cold water to the bath during the extraction in order to maintain the bath below 30 C. 6.5 Weigh, to the nearest 0,01 mg, a quantity of the reference antidegradant
34、 as close to the expected quantity of antidegradant contained in the test portion and place in a 20 cm3flask. 6.6 Add accurately, by pipette, 10 cm3of extraction solvent (3.3), stopper the flask and dissolve the reference antidegradant, using the ultrasonic bath below 30 C, if necessary. 6.7 Inject
35、into the HPLC column (4.2) a 10 mm3volume of the rubber sample extract prepared in 6.4 and elute in accordance with the programme given in 5.8. 6.8 Record the areas of the sample antidegradant peaks. 6.9 Inject into the HPLC column a 10 mm3volume of the reference antidegradant solution prepared in 6
36、.6 and elute in accordance with the programme given in 5.8. 6.10 Record the areas of the reference antidegradant peaks. 7 Expression of results Calculate the concentration of antidegradant in the sample for each of the two determinations, using the following equation: % antidegradant = sccs100mAmAwh
37、ere msis the mass, in milligrams, of the reference antidegradant test portion; mcis the mass, in milligrams, of the sample test portion; Asis the area of the reference antidegradant peaks; Acis the area of the sample antidegradant peaks. Record the average of the two results. 8 Precision See Annex A
38、. BS ISO 11089:2010ISO 11089:2010(E) 4 ISO 2010 All rights reserved9 Test report The test report shall include the following particulars: a) a reference to this International Standard; b) all details necessary for the identification of the sample; c) the concentration, in percent, of the antidegrada
39、nt in the sample; d) the date of the test. BS ISO 11089:2010ISO 11089:2010(E) ISO 2010 All rights reserved 5Annex A (informative) Precision A.1 General An interlaboratory test programme (ITP) was conducted in 2008, using the precision procedures described in ISO/TR 9272:2005, Rubber and rubber produ
40、cts Determination of precision for test method standards. Refer to this edition for further details of, and terminology used in, the determination of precision data. The ITP was conducted on two different mixes obtained by the addition of 1 part (by mass) of antidegradant to 100 parts (by mass) of S
41、BR 1500. One mix contained N-1,3-dimethylbutyl-N-phenyl-p-phenylenediamine (6PPD) while the other mix contained N,N-ditolyl-p-phenylenediamine (DTPD) (a single antidegradant in each mix). The mixes were prepared on a roll mill maintained at room temperature. Seven laboratories participated in the IT
42、P and, since the precision was determined directly on the target material with only limited preparation before the analysis, this ITP generated a type 1 precision. A.2 Precision results A.2.1 The precision results obtained for each of the two rubber mixes are given in Table A.1. These results were c
43、alculated using the outlier deletion procedures described in ISO/TR 9272:2005. Table A.1 also lists the number of laboratories remaining after the deletion of laboratories that had produced outliers. General statements on the use of the precision results are given in A.2.2 and A.2.3 for the absolute
44、 precision, r and R, and for the relative precision, (r) and (R), respectively. A.2.2 Repeatability: The repeatability, r, of the test method has been established as 0,24 percentage points. Two single test results, obtained under repeatability conditions, i.e. in the same laboratory, that differ by
45、more than 0,24 percentage points should be considered as suspect, i.e. to have come from different populations, and should suggest that some appropriate investigative action be taken. A.2.3 Reproducibility: The reproducibility, R, of the test method has been established as 0,36 percentage points. Tw
46、o single test results, obtained under reproducibility conditions, i.e. in different laboratories, that differ by more than 0,36 percentage points should be considered as suspect, i.e. to have come from different populations, and should suggest that some appropriate investigative action be taken. BS
47、ISO 11089:2010ISO 11089:2010(E) 6 ISO 2010 All rights reservedTable A.1 Precision data for percentage of antidegradants in rubber Mean level Within laboratory Between laboratories Material % srr (r) sRR (R) No. of labsa6PPD in SBR 1,04 0,06 0,16 15,4 0,15 0,41 39,5 6 DTPD in SBR 1,14 0,11 0,31 27,4
48、0,11 0,31 27,4 5 Average valueb1,09 0,08 0,24 21,4 0,13 0,36 33,4 Notation used: sris the within-laboratory standard deviation (in measurement units); r is the repeatability (in measurement units); (r) is the repeatability (as a percentage of the mean level); sRis the between-laboratory standard dev
49、iation (in measurement units); R is the reproducibility (in measurement units); (R) is the reproducibility (as a percentage of the mean level). aNumber of labs after deletion of outliers; three-step analysis; total of seven labs participated. bSimple averages calculated. BS ISO 11089:2010BS ISO 11089:2010ISO 11089:2010(E) ICS 83.040.10 Price based on 6 pages ISO 2010 All rights reserved BS ISO 11089:2010This page has been intentionally left blank
