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1、 Reference number ISO 16014-4:2003(E) ISO 2003 INTERNATIONAL STANDARD ISO 16014-4 First edition 2003-04-15 Plastics Determination of average molecular mass and molecular mass distribution of polymers using size- exclusion chromatography Part 4: High-temperature method Plastiques Dtermination de la m
2、asse molculaire moyenne et de la rpartition des masses molculaires des polymres par chromatographie dexclusion strique Partie 4: Mesurage aux tempratures leves Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/99725450
3、01 Not for Resale, 04/20/2007 04:05:53 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 16014-4:2003(E) PDF disclaimer This PDF file may contain embedded typefaces. In accordance with Adobes licensing policy, this file may be printed or viewed but shall not be edited unl
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6、n the unlikely event that a problem relating to it is found, please inform the Central Secretariat at the address given below. ISO 2003 All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means, electronic or mechanical, in
7、cluding 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 22 749 01 11 Fax + 41 22 749 09 47 E-mail copyrightiso.org Web www.iso.org Publ
8、ished in Switzerland ii ISO 2003 All rights reserved Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/20/2007 04:05:53 MDTNo reproduction or networking permitted without license from IHS
9、-,-,- ISO 16014-4:2003(E) ISO 2003 All rights reserved iii Contents Page Forewordiv 1 Scope1 2 Normative references .1 3 Terms and definitions.1 4 Principle.1 5 Reagents1 6 Apparatus.2 7 Procedure.4 8 Data acquisition and processing.6 9 Expression of results6 10 Precision6 11 Test report8 Annex A (i
10、nformative) Further information on applicability of method9 Annex B (informative) Further information on reagents 10 Bibliography .12 Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/20/2
11、007 04:05:53 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 16014-4:2003(E) iv ISO 2003 All rights reserved Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of prepari
12、ng 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, in lia
13、ison 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 Directives, Part 2. The main task of
14、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 bodies casting a vote. Attention is
15、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 16014-4 was prepared by Technical Committee ISO/TC 61, Plastics, Subcommittee SC 5, Physical- chemical propert
16、ies. ISO 16014 consists of the following parts, under the general title Plastics Determination 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 Par
17、t 4: High-temperature method Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/20/2007 04:05:53 MDTNo reproduction or networking permitted without license from IHS -,-,- INTERNATIONAL STAN
18、DARD ISO 16014-4:2003(E) ISO 2003 All rights reserved 1 Plastics Determination of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography Part 4: High-temperature method 1 Scope This part of ISO 16014 specifies a method for determining the average molec
19、ular mass and the molecular mass distribution of polymers by size-exclusion chromatography (SEC) using an organic eluent at temperatures between 60 C and 180 C. The average molecular mass and the molecular mass distribution are calculated from a calibration curve constructed using polymer standards.
20、 Therefore, this test method is classified as a relative method (see ISO 16014-1:2003, Annex A). 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest
21、edition of the referenced document (including any amendments) applies. ISO 16014-1, Plastics Determination of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography Part 1: General principles ISO 16014-2, Plastics Determination of average molecular mas
22、s and molecular mass distribution of polymers using size-exclusion chromatography Part 2: Universal calibration method 3 Terms and definitions For the purposes of this document, the terms and definitions given in ISO 16014-1 apply. 4 Principle See ISO 16014-1:2003, Clause 4. 5 Reagents 5.1 Eluent Fo
23、r a general discussion of eluents, see ISO 16014-1:2003, Subclause 5.1. For examples of eluents used for SEC measurements at temperatures above 60 C, see Annex B. Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/99725
24、45001 Not for Resale, 04/20/2007 04:05:53 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 16014-4:2003(E) 2 ISO 2003 All rights reserved 5.2 Reagent for column evaluation See ISO 16014-1:2003, Subclause 5.2. There are several low molecular mass compounds that can be use
25、d, for example diphenylmethane when 1,2-dichlorobenzene is used as eluent or ethylbenzene when 1,2,4-trichlorobenzene is used as eluent. 5.3 Molecular mass standards See ISO 16014-1:2003, Subclause 5.3. Some examples of commercially available molecular mass standards are given in Annex B. 5.4 Reagen
26、t for flow rate marker (internal standard) See ISO 16014-1:2003, Subclause 5.4. It is often very difficult to find a low molecular mass compound suitable for use as a flow rate marker because it should not co-elute with the polymer peak, the system peak or the solvent peak. An example of a compound
27、suitable for use as a flow rate marker is 2,6-di-tert-butyl-4-methylphenol when 1,2-dichlorobenzene or 1,2,4-trichlorobenzene is used as eluent. 5.5 Additives Phenol-type antioxidants such as 2,6-di-tert-butyl-4-methylphenol should preferably be added to avoid degradation of the polymer sample. For
28、further examples of antioxidants, see Annex B. 6 Apparatus 6.1 General A schematic diagram of an SEC system is shown in ISO 16014-1:2003, Figure 1. Either commercially available or assembled SEC systems can be used, provided they meet the component requirements specified and have the capability to m
29、aintain a constant column temperature between 60 C and 180 C. However, the temperature of components connected upstream of the injector, such as the eluent reservoir, the pumping system and the tubing, are not kept at the same temperature as the columns. The use of a commercially available SEC syste
30、m is recommended because of the difficulty involved in assembling a system operating at such high temperatures. 6.2 Eluent reservoir See ISO 16014-1:2003, Subclause 6.2. As mentioned in 6.1 above, it is not necessary to keep the eluent reservoir at the same temperature as the columns. Copyright Inte
31、rnational Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/20/2007 04:05:53 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 16014-4:2003(E) ISO 2003 All rights reserved 3 6.3 Pumpin
32、g system See ISO 16014-1:2003, Subclause 6.3. In order to maintain the flow rate accurate to within 0,3 %, the pumping system shall be kept at a constant temperature. It is, however, not necessary to keep the pumping system at the same temperature as the columns. 6.4 Injector See ISO 16014-1:2003, S
33、ubclause 6.4. In order to ensure that the polymer solution remains clear, without any precipitation, the injector temperature- control equipment shall be capable of keeping the injector at the same temperature, to within 1 C, as the columns. As manual injection is impossible at such temperatures, an
34、 automatic injection system shall be used. 6.5 Columns See ISO 16014-1:2003, Subclause 6.5. Organic or inorganic packing materials can be used, and there are no limitations on particle size or shape except that, when analysing high molecular mass and/or shear-sensitive polymers, the particle size sh
35、all be large enough for no rupture of the polymer chain to occur during elution of the polymers. The set of columns used shall have a theoretical plate number greater than 12 000/m and the resolution factor R shall be greater than 1,5 close to the polymer peak. The asymmetry factor shall be within t
36、he range 1,00 0,15. The set of columns used shall cover the whole range of molecular masses being determined and the calibration curve shall be as linear as possible (the correlation factor shall be very close to 1). Determination of the theoretical plate number, the resolution factor and the asymme
37、try factor of the columns shall be carried out as described in ISO 16014-1:2003, Subclause 6.5. The column temperature-control equipment shall be capable of keeping the columns within 0,5 C of the temperature set to ensure adequate reproducibility of the results. 6.6 Detector See ISO 16014-1:2003, S
38、ubclause 6.6. The detector temperature-control equipment shall be capable of keeping the detector within 0,5 C of the temperature set, in order to meet the requirements for flow rate and baseline stability (sensitivity). It is recommended that the columns and detector be kept at the same temperature
39、. 6.7 Tubing See ISO 16014-1:2003, Subclause 6.7. The temperature of the tubing shall be kept constant and high enough to ensure that the column performance requirements are met, but it is not necessary to keep the tubing at the same temperature as the column. 6.8 Temperature-control unit One of the
40、 important factors in SEC is that all components need to be kept at a constant temperature and, with the method described in this part of ISO 16014, some of them need to be kept at a high temperature. Therefore, an accurate temperature-control system is essential to meet the performance requirements
41、 for SEC. Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/20/2007 04:05:53 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 16014-4:2003(E) 4 ISO 2003 All ri
42、ghts reserved 6.9 Recorder and plotter See ISO 16014-1:2003, Subclause 6.9. 6.10 Data-processing system See ISO 16014-1:2003, Subclause 6.10. 6.11 Other components In addition to the components described above, a column guard filter, a pressure monitor, a pulse damper or other related components can
43、 be used, if necessary. 7 Procedure 7.1 Preparation of solutions of molecular mass standards The molecular mass standards used to construct the calibration curve shall be selected so as to cover the range of molecular masses of the polymer being analysed and so that there are at least two standards
44、in each molecular mass decade. Solutions may be prepared which contain more than one narrow molecular mass distribution standard, but only when the standards are perfectly separated from each other on the chromatogram. Solutions of standards of molecular mass greater than 1 000 000 shall be prepared
45、 separately. If molecular mass standards having the same chemical structure as the polymer being analysed are not available, the calibration curve may be constructed using standards consisting of a different type of polymer and a universal calibration curve constructed for this different type of pol
46、ymer (see ISO 16014-2). If gentle shaking and/or stirring or heating is required to accelerate dissolution, the time shall be as short as possible to avoid any rupture of the polymer chains. Filtration of the solutions is recommended to protect the column from clogging. In such cases, membrane filte
47、rs or sintered-metal filters with a pore size between 0,2 m and 1 m shall be used. If solid material is observed on the filter, indicating incomplete dissolution, repeat the dissolution process. If a membrane filter is used, the membrane and backing shall be inert to the solvent being used. In gener
48、al, use solutions within 48 h of preparation. However, longer storage times are allowed if the solution is kept in a cool, dark place to prevent polymer degradation and solvent evaporation. Recommended concentrations for solutions of molecular mass standards are as follows: Mp 5 104 0,4 mg/cm3 5 104 u Mp 106 0,2 mg/cm3 106 u Mp 0,1 mg/cm3 If a viscometric detector is used, higher molecular mass standard concentrations are required in the lower molecular mass region. Sample elution tim