ASTM D6953-11

Standard Test Method for Determination of Antioxidants and Erucamide Slip Additives in Polyethylene Using Liquid Chromatography (LC)

SIGNIFICANCE AND USE
Separation and identification of stabilizers used in the manufacture of polyethylene resins are necessary in order to correlate performance properties with polymer composition. This test method provides a means to determine the polymer additives listed in Table 1 in polyethylene samples. This test method is capable of the determination of other antioxidants, but the stability of these during extraction has not been investigated.
The additive extraction procedure is made effective by the relatively low solubility of the polymer sample in solvents generally used for liquid chromatographic analysis. In this method, isopropanol and cyclohexane were chosen because of their excellent extraction efficiencies as well as for safety reasons. Other solvents including ethylacetate, isobutanol, chloroform and methylene chloride can also be used.
Methods other than refluxing that have been used to remove additives from the polymer matrix including pressurized liquid, microwave, ultrasonic, and supercritical fluid extractions. For the separation of the extracted additives, SFC and GC have been used successfully for several of the additives.
Under optimum conditions, the lowest level of detection for an antioxidant is approximately 2 ppm.
SCOPE
1.1 This test method covers a liquid-chromatographic procedure for the separation of primary and secondary antioxidant and slip additives currently used in polyethylene plastics. These additives are extracted with either isopropanol (resin densities  0.94 g/cm3) or cyclohexane (resin densities > 0.94 g/cm3) prior to liquid-chromatographic separation. The ultraviolet absorbance of the eluting compound(s) is measured and quantitation is performed using external calibration.
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific precautionary statements are given in Section 9.
Note 1—There is no known ISO equivalent to this standard.

General Information

• Status: Historical
• Publication Date: 31-Aug-2011
• ICS: 83.040.20 - Rubber compounding ingredients
• Technical Committee: D20 - Plastics
• Drafting Committee: D20.70 - Analytical Methods

Relations

• Replaces: ASTM D6953-03 - Standard Test Method for Determination of Antioxidants and Erucamide Slip Additives in Polyethylene Using Liquid Chromatography (LC)
• Effective Date: 01-Sep-2011
• Replaced By: ASTM D6953-18 - Standard Test Method for Determination of Antioxidants and Erucamide Slip Additives in Polyethylene Using Liquid Chromatography (LC)
• Effective Date: 01-Nov-2018
• Referred By: ASTM D7210-21 - Standard Practice for Extraction of Additives in Polyolefin Plastics
• Effective Date: 01-Sep-2011

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation:D6953 −11
Standard Test Method for
Determination of Antioxidants and Erucamide Slip Additives
1
in Polyethylene Using Liquid Chromatography (LC)
This standard is issued under the fixed designation D6953; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope* Ultraviolet and Visible Spectrophotometers
E691 Practice for Conducting an Interlaboratory Study to
1.1 This test method covers a liquid-chromatographic pro-
Determine the Precision of a Test Method
cedure for the separation of primary and secondary antioxidant
E1657 Practice for Testing Variable-Wavelength Photomet-
and slip additives currently used in polyethylene plastics.
ric Detectors Used in Liquid Chromatography
These additives are extracted with either isopropanol (resin
3 IEEE/ASTM SI 10 Standard for Use of the International
densities < 0.94 g/cm ) or cyclohexane (resin densities > 0.94
3 System of Units (SI): The Modern Metric System
g/cm ) prior to liquid-chromatographic separation. The ultra-
violet absorbance of the eluting compound(s) is measured and
3. Terminology
quantitation is performed using external calibration.
3.1 Definitions:
1.2 The values stated in SI units are to be regarded as
3.1.1 For definitions of plastic terms and detector terminol-
standard. No other units of measurement are included in this
ogy used in this test method, see Terminologies D883, D1600,
standard.
and E1657.
1.3 This standard does not purport to address all of the
3.1.2 Forunitsandsymbolsusedinthistestmethod,referto
safety concerns, if any, associated with its use. It is the
Terminology E131 or IEEE/ASTM SI 10.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
4. Summary of Test Method
bility of regulatory limitations prior to use. Specific precau-
4.1 The polyethylene sample is ground to a 1-mm (~20
tionary statements are given in Section 9.
mesh) or 0.5-mm (~40 mesh) particle size and extracted by
NOTE 1—There is no known ISO equivalent to this standard.
refluxing with either isopropanol or cyclohexane.
4.2 The solvent extract is analyzed by liquid chromatogra-
2. Referenced Documents
phy.
2
2.1 ASTM Standards:
4.3 Additive concentrations are determined from external
D883 Terminology Relating to Plastics
calibration curves using reverse phase chromatography (C-8 or
D1600 Terminology forAbbreviatedTerms Relating to Plas-
C-18 column) with ultraviolet (UV) detection at wavelengths
tics
corresponding to the wavelengths of an absorption apex of
D4697 Guide for Maintaining Test Methods in the User’s
3
each additive (except erucamide which does not have an
Laboratory (Withdrawn 2009)
absorption maximum in the accessible UV region).
E131 Terminology Relating to Molecular Spectroscopy
E169 PracticesforGeneralTechniquesofUltraviolet-Visible
5. Significance and Use
Quantitative Analysis
E275 Practice for Describing and Measuring Performance of
5.1 Separation and identification of stabilizers used in the
manufacture of polyethylene resins are necessary in order to
correlate performance properties with polymer composition.
1
This test method is under the jurisdiction ofASTM Committee D20 on Plastics
This test method provides a means to determine the polymer
and is the direct responsibility of Subcommittee D20.70 on Analytical Methods.
additives listed in Table 1 in polyethylene samples. This test
Current edition approved Sept. 1, 2011. Published September 2011. Originally
approved in 2003. Last previous edition approved in 2003 as D6953 - 03.
method is capable of the determination of other antioxidants,
DOI:10.1520/D6953-11.
but the stability of these during extraction has not been
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
investigated.
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
5.2 The additive extraction procedure is made effective by
the ASTM website.
3
the relatively low solubility of the polymer sample in solvents
The last approved version of this historical standard is referenced on
www.astm.org. generally used for liquid chromatographic analysis. In this
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

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D6953−11
TABLE 1 Common Polyolefin Additives
Chemical Name Chemical Classification CAS Number
Formula
BHEB, 2,6-di-t-butyl-4-ethylphenol or
...

This document is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation:D6953–03 Designation: D6953 – 11
Standard Test Method for
Determination of Antioxidants and Erucamide Slip Additives
1
in Polyethylene Using Liquid Chromatography (LC)
This standard is issued under the fixed designation D6953; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope
1.1This test method covers a liquid-chromatographic procedure for the separation of some additives currently used in
*
polyethylene. These additives are extracted with either isopropanol (resin densities < 0.94 g/cm
1.1 This test method covers a liquid-chromatographic procedure for the separation of primary and secondary antioxidant and
slip additives currently used in polyethylene plastics. These additives are extracted with either isopropanol (resin densities < 0.94
3
3
g/cm ) or cyclohexane (resin densities > 0.94 g/cm ) prior to liquid-chromatographic separation. The ultraviolet absorbance of the
eluting compound(s) is measured and quantitation is performed using external calibration.
1.2
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use. Specific precautionary statements are given in Section 9.
NOTE1—There is no equivalent ISO standard. 1—There is no known ISO equivalent to this standard.
2. Referenced Documents
2
2.1 ASTM Standards:
D883 Terminology Relating to Plastics
D1600 Terminology for Abbreviated Terms Relating to Plastics
D4697 Guide for Maintaining Test Methods in the User’s Laboratory
E131 Terminology Relating to Molecular Spectroscopy
E169 Practices for General Techniques of Ultraviolet-Visible Quantitative Analysis
E275 Practice for Describing and Measuring Performance of Ultraviolet and Visible Spectrophotometers
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
E1657 Practice for Testing Variable-Wavelength Photometric Detectors Used in Liquid Chromatography
IEEE/ASTM SI 10 Standard for Use of the International System of Units (SI): The Modern Metric System
3. Terminology
3.1 Definitions:
3.1.1 For definitions of plastic terms and detector terminology used in this test method, see Terminologies D883, D1600, and
E1657.
3.1.2 For units and symbols used in this test method, refer to Terminology E131 or IEEE/ASTM SI 10.
3.2Additives:
3.2.1BHEB, Prodox 500—2,6-di-t-butyl-4-ethylphenol or butylated hydroxyethyl benzene, CAS No. 4130-42-1.
3.2.2BHT, CAO-3, Noclizer M-17—2,6-di-t-butylcresol or butylated hydroxy toluene, CAS No. 128-37-0.
3.2.3Irgafos 168—Tris(2,4-di-t-butylphenyl)-phosphite, CAS No. 31570-04-4.
3.2.3.1Oxidized Irgafos 168—Tris(2,4-di-t-butylphenyl)-phosphate.
3.2.4Irganox 1010—Tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane CAS No. 6683-19-8.
3.2.5Irganox 1076—Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, CAS No. 2082-79-3.
1
This test method is under the jurisdiction of ASTM Committee D20 on Plastics and is the direct responsibility of Subcommittee D20.70 on Analytical Methods.
Current edition approved July 10, 2003. Published August 2003. DOI: 10.1520/D6953-03.
Current edition approved Sept. 1, 2011. Published September 2011. Originally approved in 2003. Last previous edition approved in 2003 as D6953 - 03.
DOI:10.1520/D6953-11.
2
For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at [e-mail]. For Annual Book ofASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this standard.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
1

---------------------- Page: 1 ----------------------
D6953 – 11
3.2.6Isonox 129—2,2’-ethylidene bis(4,6-di-t-butylphenol), CAS No. 112-84-5.
3.2.7Kemamide-E, Erucamide—Cis-13-docosenamide, CAS No. 112-84-5.
3.2.8TNPP, Weston 399—Tris(nonylphenyl)phosphite, CAS No. 26523-78-4.
3.2.8.1Hydrolyzed TNPP—Nonylphenol, CAS No. 104-40-
...