ISO 16014-4:2003

Plastics — Determination of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography — Part 4: High-temperature method

ISO 16014-4:2003 specifies a method for determining the average molecular 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. Therefore this method is classified as a relative method.

Plastiques — Détermination de la masse moléculaire moyenne et de la répartition des masses moléculaires des polymères par chromatographie d'exclusion stérique — Partie 4: Mesurage aux températures élevées

General Information

• Status: Withdrawn
• Publication Date: 14-Apr-2003
• Withdrawal Date: 14-Apr-2003
• ICS: 83.080.01 - Plastics in general
• Technical Committee: ISO/TC 61/SC 5 - Physical-chemical properties
• Drafting Committee: ISO/TC 61/SC 5/WG 11 - Analytical methods
• Current Stage: 9599 - Withdrawal of International Standard
• Completion Date: 03-Jul-2012

Relations

• Revised: ISO 16014-4:2012 - Plastics — Determination of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography — Part 4: High-temperature method
• Effective Date: 18-Dec-2008

Standards Content (Sample)

INTERNATIONAL ISO
STANDARD 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 — Détermination de la masse moléculaire moyenne et de la
répartition des masses moléculaires des polymères par
chromatographie d'exclusion stérique —
Partie 4: Mesurage aux températures élevées




Reference number
ISO 16014-4:2003(E)
©
ISO 2003

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ISO 16014-4:2003(E)
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ii © ISO 2003 — All rights reserved

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ISO 16014-4:2003(E)
Contents Page
Foreword. iv
1 Scope. 1
2 Normative references . 1
3 Terms and definitions. 1
4 Principle . 1
5 Reagents . 1
6 Apparatus. 2
7 Procedure. 4
8 Data acquisition and processing. 6
9 Expression of results. 6
10 Precision . 6
11 Test report. 8
Annex A (informative) Further information on applicability of method . 9
Annex B (informative) Further information on reagents . 10
Bibliography . 12

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ISO 16014-4:2003(E)
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 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
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 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 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 properties.
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
 Part 4: High-temperature method
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INTERNATIONAL STANDARD ISO 16014-4:2003(E)

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 molecular 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. 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 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 mass 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
For 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.
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ISO 16014-4:2003(E)
5.2 Reagent for column evaluation
See ISO 16014-1:2003, Subclause 5.2.
There are several low molecular mass compounds that can be used, 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 Reagent 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 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 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 maintain 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 system 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.
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ISO 16014-4:2003(E)
6.3 Pumping 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, Subclause 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 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 shall 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 the 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 asymmetry 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, Subclause 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.
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 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
for SEC.
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ISO 16014-4:2003(E)
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 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 in each
molecular mass decade. Solu
...