BS EN ISO 16014-5-2012 Plastics Determination of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography Method using light-scatterin.pdf

1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN ISO 16014-5:2012Plastics Determination ofaverage molecular mass andmolecular mass distribution ofpolymers using size-exclusionchromatographyPart 5: Method using light-scatt

2、eringdetection (ISO 16014-5:2012)BS EN ISO 16014-5:2012 BRITISH STANDARDNational forewordThis British Standard is the UK implementation ofEN ISO 16014-5:2012.The UK participation in its preparation was entrusted to Technical Committee PRI/21, Testing of plastics.A list of organizations represented o

3、n 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 2012. Published by BSI Standards Limited 2012ISBN 978 0 580 65053

4、 6 ICS 83.080.01 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 2012.Amendments issued since publicationDate T e x t a f f e c t e dEUROPEAN STANDARD NO

5、RME EUROPENNE EUROPISCHE NORM EN ISO 16014-5 July 2012 ICS 83.080.01 English Version Plastics - Determination of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography - Part 5: Method using light-scattering detection (ISO 16014-5:2012) Plastiques - Dt

6、ermination de la masse molculaire moyenne et de la distribution des masses molculaires de polymres par chromatographie dexclusion strique - Partie 5: Mthode utilisant la dtection par diffusion lumineuse (ISO 16014-5:2012) Kunststoffe - Bestimmung der durchschnittlichen Molmasse und der Molmassenvert

7、eilung von Polymeren mittels Gelpermeationschromatographie - Teil 5: Lichtstreudetektionsverfahren (ISO 16014-5:2012) This European Standard was approved by CEN on 30 June 2012. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this E

8、uropean Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official vers

9、ions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria,

10、 Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, S

11、witzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2012 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Member

12、s. Ref. No. EN ISO 16014-5:2012: EBS EN ISO 16014-5:2012EN ISO 16014-5:2012 (E) 3 Foreword This document (EN ISO 16014-5:2012) has been prepared by Technical Committee ISO/TC 61 “Plastics“ in collaboration with Technical Committee CEN/TC 139 “Paints and varnishes” the secretariat of which is held by

13、 DIN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by January 2013, and conflicting national standards shall be withdrawn at the latest by January 2013. Attention is drawn to the possibility that

14、some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to i

15、mplement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Roma

16、nia, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of ISO 16014-5:2012 has been approved by CEN as a EN ISO 16014-5:2012 without any modification. BS EN ISO 16014-5:2012ISO 16014-5:2012(E) ISO 2012 All rights reserved iiiContents PageForeword . v1

17、 Scope 12 Normative references . 13 Terms and definitions . 14 Symbols . 25 Principle . 25.1 SEC 25.2 Light-scattering SEC 26 Reagents 26.1 Eluent 26.2 Reagent for column evaluation . 36.3 Calibration standards . 36.4 Reagent for flow rate marker 36.5 Additives 37 Apparatus 37.1 General . 37.2 Eluen

18、t reservoir . 47.3 Pumping system 47.4 Injector . 47.5 Columns . 47.6 Detector 57.7 Tubing . 57.8 Temperature control . 57.9 Recorder and plotter . 57.10 Data-processing system 57.11 Other components 58 Procedure 58.1 Preparation of calibration solutions . 58.2 Preparation of a solution for determin

19、ing the L-point . 58.3 Preparation of sample solutions . 58.4 Preparation of solutions for column performance evaluation 68.5 Setting up the apparatus . 68.6 Operating parameters 68.7 Number of determinations 69 Calibration . 69.1 Calibration of concentration-sensitive detector and light-scattering

20、detector 69.2 Determination of delay volume 89.3 Normalization of detector sensitivity . 89.4 Determination of refractive index increment . 810 Data acquisition and processing 810.1 Data acquisition . 810.2 Evaluation of data and correction of chromatograms 810.3 Data processing . 911 Expression of

21、results .1011.1 Calibration curve .1011.2 Calculation of average molecular mass 1211.3 Differential molecular mass distribution curve .1211.4 Cumulative molecular mass distribution curve 1212 Precision 1313 Test report .13BS EN ISO 16014-5:2012ISO 16014-5:2012(E)iv ISO 2012 All rights reserved13.1 G

22、eneral .1313.2 Apparatus and measurement parameters 1313.3 Calibration of the system 1313.4 Calibration curve .1413.5 Results .14Annex A (informative) Round-robin test .15Annex B (informative) Information on light scattering .17Annex C (informative) Calibration curve in low molecular mass range 21Bi

23、bliography .23BS EN ISO 16014-5:2012ISO 16014-5:2012(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 normally carried out through ISO technical committees.

24、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 in the work. ISO collaborates closely with the Internat

25、ional Electrotechnical 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 Standar

26、ds 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 bodies casting a vote.Attention is drawn to the possibility that some of the elements of this document may be the subject o

27、f patent rights. ISO shall not be held responsible for identifying any or all such patent rights.ISO 16014-5 was prepared by Technical Committee ISO/TC 61, Plastics, Subcommittee SC 5, Physical-chemical properties.ISO 16014 consists of the following parts, under the general title Plastics Determinat

28、ion of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography: Part 1: General principles Part 2: Universal calibration method Part 3: Low-temperature method Part 4: High-temperature method Part 5: Method using light-scattering detection ISO 2012 All r

29、ights reserved vBS EN ISO 16014-5:2012BS EN ISO 16014-5:2012Plastics Determination of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography Part 5: Method using light-scattering detection1 ScopeThis part of ISO 16014 specifies a general method for det

30、ermining the average molecular mass and the molecular mass distribution of polymers using SEC-LS, i.e. size-exclusion chromatography coupled with light-scattering detection. The average molecular mass and the molecular mass distribution are calculated from molecular mass data and mass concentrations

31、 determined continuously with elution time. The molecular mass at each elution time is determined absolutely by combining a light-scattering detector with a concentration-sensitive detector. Therefore, SEC-LS is classified as an absolute method.For the applicability of the method, see ISO 16014-1:20

32、12, Clause A.1.2 Normative referencesThe following referenced documents are indispensable for the application 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 472, Plas

33、tics VocabularyISO 16014-1:2012, Plastics Determination of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography Part 1: General principlesISO 16014-2, Plastics Determination of average molecular mass and molecular mass distribution of polymers using

34、size-exclusion chromatography Part 2: Universal calibration methodISO 16014-3:2012, Plastics Determination of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography Part 3: Low-temperature methodISO 16014-4:2012, Plastics Determination of average molec

35、ular mass and molecular mass distribution of polymers using size-exclusion chromatography Part 4: High-temperature method3 Terms and definitionsFor the purposes of this document, the terms and definitions given in ISO 472 and ISO 16014-1 and the following apply.3.1light-scattering detectionLS detect

36、iona technique for determining the mass or size of polymer molecules in solution by measuring the light scattered by the polymer moleculesINTERNATIONAL STANDARD ISO 16014-5:2012(E) ISO 2012 All rights reserved 1BS EN ISO 16014-5:2012ISO 16014-5:2012(E)3.2refractive index incrementdn/dcrate of change

37、 of the refractive index n of a polymer solution as a function of the mass concentration cNOTE 1 It is also called the “specific refractive index increment” in the literature.NOTE 2 The limiting value of dn/dc at zero concentration is commonly used in light scattering.3.3L-pointmeasured data point o

38、f a low molecular mass compound on the graph of molecular mass vs. elution time used for justification of the polynominal fit of the calibration curve and/or construction of the calibration curve.NOTE In the lower molecular mass region, the LS signal is too low to calculate molecular mass. Therefore

39、 the measurement of the L-point is needed for justification or construction of the molecular mass calibration curve for the whole range of molecular mass. The L-point is determined by measuring an oligomer of the polymer or an organic compound with a similar chemical structure to the oligomer.4 Symb

40、olsRgradius of gyration of a polymer molecule in solution nmA2second virial coefficient for a polymer molecule in solution cm3molg2c mass concentration of polymer in solution gcm3dn/dc refractive index increment cmg1Hiexcess signal intensity of a concentration detector at the ith elution time ILS,ie

41、xcess signal intensity of scattered light at the ith elution time Vevolume eluted during data acquisition time (interval) cm35 Principle5.1 SECFor a discussion of size-exclusion chromatography in general, see ISO 16014-1:2012, Clause 4.5.2 Light-scattering SECIn SEC-LS, polymer molecules eluted from

42、 the SEC columns are irradiated by a beam of monochromatic visible light. The light scattered by the molecules is continuously detected by a light-scattering detector. Since the eluate is a dilute polymer solution, the intensity of the scattered light is approximately proportional to the product of

43、the molecular mass and the mass concentration of the polymer molecules. The scattered-light intensity divided by the concentration therefore gives the molecular mass at a particular elution time. The values of the molecular mass and the mass concentration or mass fraction at each elution time are us

44、ed to calculate the molecular mass distribution and the average molecular mass of the polymer.6 Reagents6.1 EluentFor a general discussion of eluents, see ISO 16014-1:2012, 5.1.For examples of eluents used for SEC measurements at temperatures below and above 60 C, see Annex B of ISO 16014-3:2012 and

45、 Annex B of ISO 16014-4:2012, respectively.2 ISO 2012 All rights reservedBS EN ISO 16014-5:2012ISO 16014-5:2012(E)6.2 Reagent for column evaluationFor examples of low molecular mass compounds used for column evaluation, see ISO 16014-3:2012, 5.2, for measurements at temperatures below 60 C and ISO 1

46、6014-4:2012, 5.2, for those above 60 C.6.3 Calibration standardsSince the Rayleigh ratios of toluene and benzene are well-known, these solvents are recommended for determining the calibration constant of the light-scattering detector (see Annex B, Clause B.2).Aqueous solutions of potassium chloride

47、(KCl) or sodium chloride (NaCl) are used for determining the calibration constant of a refractive index detector. The concentration dependence of the differential refractive index of the solutions is used to calculate the constant.A low molecular mass, monodisperse polymer is used to determine the d

48、elay volume between the light-scattering and concentration-sensitive detectors. This polymer may also be used to calibrate the angular dependence of the detector sensitivity of a multiple-angle light-scattering detector. The radius of gyration Rgof the polymer molecule used to calibrate the detector

49、 sensitivity, should preferably be less than 10 nm. A radius of gyration less than 5 nm is desirable. Other compounds with a well-known Rgvalue may also be used.Polymer reference materials are used for molecular mass calibration ranges from 20 000 to 50 000.Low molecular mass organic compounds or oligomers of the polymer in the sample under investigation are used for determining the “L-point”.6.4 Reagent for flow rate markerSee ISO 16014-1:2012, 5.4.For examples of compounds suitable for use as a flow rate marker, see