ASTM D5815-95(2001)e1
(Test Method)Standard Test Method for Determination of Phenolic Antioxidants and Erucamide Slip Additives in Linear Low-Density Polyethylene Using Liquid Chromatograph (LC) (Withdrawn 2009)
Standard Test Method for Determination of Phenolic Antioxidants and Erucamide Slip Additives in Linear Low-Density Polyethylene Using Liquid Chromatograph (LC) (Withdrawn 2009)
SIGNIFICANCE AND USE
Separation and identification of stabilizers used in the manufacture of linear low-density polyethylene are necessary in order to correlate performance properties with polymer composition. This test method provides a means to determine BHT, BHEB, Isonox 129, erucamide slip, Irganox 1010, and Irganox 1076 levels in linear low-density polyethylene samples. This test method should be applicable for the determination of other antioxidants such as Ultranox 626, Ethanox 330, Santanox R, and Topanol CA, but the applicability of this test method has not been investigated for these antioxidants.
The additive extraction procedure is made effective by the insolubility of the polymer sample in solvents generally used for liquid chromatographic analysis.
Under optimum conditions, the lowest level of detection for a phenolic antioxidant is approximately 2 ppm.
Other methods that have been successfully used to remove additives from the plastics matrix include thin film, microwave, ultrasonic, and supercritical fluid extractions. Other methods have been successfully used to separate additive including SFC and GC.
SCOPE
1.1 This test method covers a liquid-chromatographic procedure for the separation of some additives currently used in linear low-density polyethylene. These additives are extracted with either isobutanol or isopropanol prior to liquid-chromatographic separation. The ultraviolet absorbance (200 nm) of the compound(s) is measured; quantitation is performed using the internal standard method.
1.2 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 equivalent ISO standard.
WITHDRAWN RATIONALE
This test method covered a liquid-chromatographic procedure for the separation of some additives currently used in linear low-density polyethylene. These additives are extracted with either isobutanol or isopropanol prior to liquid-chromatographic separation. The ultraviolet absorbance (200 nm) of the compound(s) is measured; quantitation is performed using the internal standard method.
Formerly under the jurisdiction of Committee D20 on Plastics, this test method was withdrawn in February 2009 and replaced by Test Method D 6953 for Determination of Antioxidants and Erucamide Slip Additives in Polyethylene Using Liquid Chromatography (LC).
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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
e1
Designation:D5815–95 (Reapproved 2001)
Standard Test Method for
Determination of Phenolic Antioxidants and Erucamide Slip
Additives in Linear Low-Density Polyethylene Using Liquid
Chromatography (LC)
This standard is issued under the fixed designation D 5815; 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 (e) indicates an editorial change since the last revision or reapproval.
e NOTE—Several sections were changed editorially in March 2001.
1. Scope 3.2 For units, symbols, and abbreviations used in this test
method refer to Terminology E 131 or IEEE/ASTM SI-10.
1.1 This test method covers a liquid-chromatographic pro-
3.3 Abbreviations:Abbreviations:
cedure for the separation of some additives currently used in
3.3.1 BHEB—2,6-di-t-butyl-4-ethyl-phenol or butylated hy-
linear low-density polyethylene. These additives are extracted
droxyethyl benzene.
with either isobutanol or isopropanol prior to liquid-
3.3.2 BHT—2,6-di-t-butyl-cresol or butylated hydroxy tolu-
chromatographic separation. The ultraviolet absorbance (200
ene.
nm)ofthecompound(s)ismeasured;quantitationisperformed
3.3.3 LC—Liquid chromatography.
using the internal standard method.
3.3.4 LLDPE—Linear low-density polyethylene.
1.2 This standard does not purport to address all of the
3.4 Trade Names:
safety concerns, if any, associated with its use. It is the
3.5 Irganox 1010—Tetrakis[methylene(3,5-di-t-butyl-4-
responsibility of the user of this standard to establish appro-
hydroxy hydrocinnamate)]methane.
priate safety and health practices and determine the applica-
3.6 Irganox 1076—Octadecyl-3,5-di-t-butyl-4-hydroxy hy-
bility of regulatory limitations prior to use. Specific precau-
drocinnamate.
tionary statements are given in Section 9.
3.7 Isonox 129 —2,28-ethylidene bis (4,6-di-t-butyl phe-
NOTE 1—There is no equivalent ISO standard.
nol).
3.8 Kemamide-E—Cis-13-docosenamide, erucamide.
2. Referenced Documents
3.9 Tinuvin P—2(28-hydroxy-58-methyl phenyl)benzotriaz-
2.1 ASTM Standards:
ole.
D 883 Terminology Relating to Plastics
D 1600 Terminology for Abbreviated Terms Relating to
4. Summary of Test Method
Plastics
4.1 The LLDPE sample is ground to a 20-mesh particle size
E 131 Terminology Relating to Molecular Spectroscopy
and extracted by refluxing with either isobutanol or isopro-
E 691 Practice for Conducting an Interlaboratory Study to
panol.
Determine the Precision of a Test Method
4.2 The solvent extract is analyzed by liquid chromatogra-
IEEE/ASTM SI-10 Standard for Use of the International
phy.
System of Units (SI): The Modern Metric System
4.3 Additive concentrations are determined relative to an
internal standard (contained in the solvent) using reverse phase
3. Terminology
chromatography(C-18column)withultraviolet(UV)detection
3.1 Definitions:
at 200 nm.
3.1.1 For definitions of plastic terms used in this test
NOTE 2—Isopropanol is recommended as the extraction solvent for
method, see Terminologies D 883 and D 1600.
lower crystallinity LLDPE (0.925 density and below) and isobutanol is
recommended as the extraction solvent for higher crystallinity LLDPE
containing Irganox 1010.
This test method is under the jurisdiction ofASTM Committee D20 on Plastics
and is the direct responsibility of Subcommittee D20.70Analytical Methods.
Current edition approved Oct. 10, 1995. Published December 1995.
Annual Book of ASTM Standards, Vol 08.01.
Annual Book of ASTM Standards, Vol 03.06.
Annual Book of ASTM Standards, Vol 14.02.
5 6
Annual Book of ASTM Standards, Vol 14.04. CAS No. 112–84–5.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D5815
5. Significance and Use 8. Reagents and Materials
5.1 Separation and identification of stabilizers used in the 8.1 Tinuvin-P, 2(28hydroxy-58-methyl phenyl)benzotriaz-
manufacture of linear low-density polyethylene are necessary ole.
in order to correlate performance properties with polymer 8.2 Isobutanol:
composition. This test method provides a means to determine 8.2.1 Isobutanol T-P, HPLC grade, spectroquality or chro-
BHT, BHEB, Isonox 129, erucamide slip, Irganox 1010, and matography quality reagent isobutanol with approximately 50
Irganox 1076 levels in linear low-density polyethylene mg/L (to the nearest 0.1 mg) of Tinuvin-P added as an internal
samples. This test method should be applicable for the deter- standard.
mination of other antioxidants such as Ultranox 626, Ethanox 8.2.2 Isobutanol, HPLC grade, spectroquality or chroma-
330, Santanox R, and Topanol CA, but the applicability of this tography quality reagent.
test method has not been investigated for these antioxidants. 8.3 Isopropanol:
5.2 The additive extraction procedure is made effective by 8.3.1 Isopropanol T-P, HPLC grade, spectroquality or chro-
the insolubility of the polymer sample in solvents generally matography quality reagent isopropanol with approximately 50
used for liquid chromatographic analysis. mg/L (to the nearest 0.1 mg) mg/L of Tinuvin-P added as an
internal standard.
5.3 Under optimum conditions, the lowest level of detection
8.3.2 Isopropanol, HPLC grade, spectroquality or chroma-
for a phenolic antioxidant is approximately 2 ppm.
tography quality reagent.
5.4 Other methods that have been successfully used to
8.4 Water, HPLC, or UV quality reagent, degassed by
remove additives from the plastics matrix include thin film,
sparging with high-purity helium or by filtration under
microwave, ultrasonic, and supercritical fluid extractions.
vacuum.
Othermethodshavebeensuccessfullyusedtoseparateadditive
8.5 Acetonitrile, HPLC, spectroquality or chromatography
including SFC and GC.
quality reagent (a reagent whose UV cutoff is about 190 nm).
6. Interferences
9. Safety Precautions
6.1 Any material eluting at or near the same retention time
9.1 Isopropanol and isobutanol are flammable. This extrac-
as the additive can cause erroneous results.Apolymer-solvent-
tion procedure should be carried out in a fume hood.
extract solution containing no internal standard should be
examined to minimize the possibility of interferences.
10. Preparation of Liquid Chromatograph
6.2 A major source of interferences can be from solvent
10.1 Set the chromatograph to operate at the following
impurities. For this reason, the solvents should be examined
conditions:
prior to use by injecting a sample of solvent on the HPLC
system and analyzing as in Section 10. NOTE 3—AVydac 201HS5415, separations group, was used in this test
method. The gradient described in 10.1 provides complete separation of
antioxidants and slip using this C-18 column. If another column is used
7. Apparatus
then a different gradient may be needed to provide a complete separation
7.1 Liquid Chromatograph, equipped with a variable wave-
of the additives.
length ultraviolet detector, heated column, and gradient elution
10.1.1 Initial Mobile Phase Condition—50 % acetonitrile:
capabilities. The liquid chromatograph should be equipped
50 % water.
with a means for a 10-µL sample-solution injection such as a
10.1.2 Final Mobile Phase Condition—100 % acetonitrile:
sample loop.
0 % water.
7.2 Chromatographic Column, RP-18, 5-µm particle size,
10.1.3 Gradient Length—11 min.
15 cm by 4.6 mm.
10.1.4 Gradient Curve—Linear.
7.3 Computer System or Integrator, coupled with the chro-
10.1.5 Flow Rate—1.0 mL/min.
matograph to measure peak area.
10.1.6 Hold at 100 % Acetonitrile—0 % water for 8 min.
7.4 Wiley Mill, equipped with a 20-mesh screen and water-
10.1.7 At 19.1-Min Return to 5
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