ASTM D4443-95(2002)
(Test Method)Standard Test Method for Determining Residual Vinyl Chloride Monomer Content in PPB Range in Vinyl Chloride Homo- and Co-Polymers by Headspace Gas Chromatography
Standard Test Method for Determining Residual Vinyl Chloride Monomer Content in PPB Range in Vinyl Chloride Homo- and Co-Polymers by Headspace Gas Chromatography
SIGNIFICANCE AND USE
Vinyl chloride-containing polymers are widely used to package a variety of materials, including foods.
Vinyl chloride monomer has been shown to be a human carcinogen. Threshold toxicity value has not been established.
Plastic manufacturers, food packagers, government agencies, etc. have a need to know the residual vinyl chloride monomer content of vinyl chloride-containing polymers.
SCOPE
1.1 This test method is suitable for determining the residual vinyl chloride monomer (RVM) content of homopolymer and copolymers of vinyl chloride down to a level of 5 ppb.
1.2 This test method is applicable to any polymer form, such as resin, compound, film, bottle wall, etc. that can be dissolved in a suitable solvent.
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 hazard statements are given in Section 9 and Note 13.
Note 1—There is no similar or equivalent ISO standard.
General Information
Relations
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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:D4443–95 (Reapproved 2002)
Standard Test Method for
Determining Residual Vinyl Chloride Monomer Content in
PPB Range in Vinyl Chloride Homo- and Co-Polymers by
Headspace Gas Chromatography
This standard is issued under the fixed designation D4443; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope The response of vinyl chloride monomer is determined by the
use of one of several suggested detectors.
1.1 This test method is suitable for determining the residual
4.4 Calibration is accomplished using either (a) vinyl chlo-
vinyl chloride monomer (RVM) content of homopolymer and
ride monomer in nitrogen gas standards, (b) standard solutions
copolymers of vinyl chloride down to a level of ;5 ppb.
containingknownamountsofvinylchloridemonomer,or (c)a
1.2 Thistestmethodisapplicabletoanypolymerform,such
method of standard addition.
asresin,compound,film,bottlewall,etc.thatcanbedissolved
in a suitable solvent.
5. Significance and Use
1.3 This standard does not purport to address all of the
5.1 Vinyl chloride-containing polymers are widely used to
safety concerns, if any, associated with its use. It is the
package a variety of materials, including foods.
responsibility of the user of this standard to establish appro-
5.2 Vinyl chloride monomer has been shown to be a human
priate safety and health practices and determine the applica-
carcinogen. Threshold toxicity value has not been established.
bility of regulatory limitations prior to use. Specific hazard
5.3 Plastic manufacturers, food packagers, government
statements are given in Section 9 and Note 13.
agencies, etc. have a need to know the residual vinyl chloride
NOTE 1—There is no similar or equivalent ISO standard.
monomer content of vinyl chloride-containing polymers.
2. Referenced Document
6. Interferences
2.1 OSHA Standard:
6.1 N,N-dimethylacetamideshouldbeanalyzedunderiden-
29 CFR 1919.1017—Vinyl Chloride
ticalconditionstodeterminetheabsenceofinterferencesatthe
vinyl chloride monomer gas chromatography (GC) retention
3. Terminology
time.
3.1 Abbreviations:Abbreviations:
6.2 Other solvents, monomers, or compounding aids may
3.1.1 DMAc—N,N-dimethylacetamide.
cause interference at the vinyl chloride monomer GC retention
3.1.2 VCM—Vinyl chloride monomer.
time.
4. Summary of Test Method
7. Apparatus
4.1 Samples of vinyl chloride-containing polymers are dis-
7.1 Gas Chromatography, equipped with either a flame
solved in a suitable solvent in a closed system.
ionization detector (FID), a photo ionization detector (PID), or
4.2 The polymer solution and headspace are equilibrated at
a Hall electroconductivity detector (HED), backflushing valve,
an elevated temperature.
and either automatic capability or manual sampling (Note 2)
4.3 Aliquots of headspace gas are injected into a gas
and ability to analyze the headspace vapors contained in a
chromatograph and the vinyl chloride monomer is separated.
sealed vial.
NOTE 2—If the analyses are to be performed manually (that is, by
ThistestmethodisunderthejurisdictionofASTMCommitteeD20onPlastics syringe injection), then the following equipment will also be needed:
and is the direct responsibility of Subcommittee D20.70 on Analytical Methods
(1) Constant-temperature bath or oven capable of maintaining a
(Section D20.70.03).
temperature of 90 6 1°C.
Current edition approved October 10, 1995. Published December 1995. Origi-
(2) Gas-tight GC syringes for sampling and injection.
e1
nally published as D4443–84. Last previous edition D 4443–84(1989) .
(3) Sample bottles with fluoropolymer faces septa and caps (size
This revision includes the addition of an ISO equivalency statement and a
optional).
keywords section.
(4) Gloves for handling hot syringes.
Available from Superintendent of Documents, US Government Printing Office,
Washington, DC 20402.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D4443–95 (2002)
7.2 Chromatographic Column, 3% OV-101 on 80/100 9.1.1 Vinyl chloride monomer is a carcinogen and exposure
mesh ChromosorbWHP , ⁄8-in. (3.2-mm) outside diameter by byinhalationordermalcontact,orboth,istobeavoided.Refer
2 ft (0.6 m), stainless steel connected through ⁄8-in. “tee” to to OSHA Standard29 CFR 1919.1017 for regulated levels of
0.19% picric acid on 80/100 mesh Carbopack C , ⁄8-in. exposure. N,N-dimethylacetamide is a teratogen. The use of a
outside diameter by 8 ft (2.4 m), stainless steel. properly functioning hood and septum-sealed sample contain-
ers are recommended.
NOTE 3—Any column packing that will resolve VCM from interfer-
9.1.2 Avoid all contact with heated parts of the gas chro-
ences and elute VCM in a reasonable length of time (1 to 5 min) is
matograph, hot syringes, and sample bottles. Handle all elec-
satisfactory. For example, a 3-ft (0.9-m) by ⁄8-in. (3.2-mm) outside
trical connections with care.
diameter column containing 0.19% picric acid on 80/100 mesh Carbo-
pack C can replace the recommended 3% OV−101 column. Settings
9.1.3 Once heated, sample vials are under pressure. After
recommended in 11.3.1 may have to be modified to suit the packing
analysis,relievethepressurewithahypodermicsyringeneedle
material being used.
vented into a charcoal slug or vent tube leading to a hood
NOTE 4—The VCM peak must be kept on scale to manually measure
before removing vials from the water bath.
thecorrectpeakareaorpeakheight.Onemethodofachievingthiswithout
undue operator attention is to use a dual-channel recorder. One channel is
10. Sampling and Storage
set at a high sensitivity to obtain measurable small peaks for low-VCM
samples. The other channel is set at a lower sensitivity to keep the larger
10.1 Keep all polymer samples in tightly sealed jars or
peaks from high-VCM samples on scale. Most instruments will calculate
tightly wrapped aluminum foil prior to analysis. Dissolved
peak height (or area) even if the peak goes off the scale on the recorder.
polymersamplesmustbekeptinseptum-sealedvialsorbottles
7.3 Detector Output Filter/Amplifier—The extreme sensi-
until analyzed. Polymer solutions stored longer than 24 h
tivity of this test method is best realized when the detector should be maintained under refrigeration.
(usually operated at the maximum sensitivity) output is (1)
11. Preparation of Gas Chromatograph
filteredtoremovethehigh-frequencynoiseand(2)amplifiedto
give a visible or measurable signal. The filter/amplifier is
NOTE 8—All conditions in this section refer to the Perkin-Elmer
connected in series between the detector and the recorder/
Headspace Analyzer. If analyses are performed manually, alter the
computer.
operating procedures as required by the instrumentation.
11.1 Install the chromatographic column and condition
NOTE 5—A Spectrum Scientific Model 1021A filter/amplifier can
overnight at 100°C, using normal carrier flow. Do not connect
fulfill these requirements. Other filter/amplifiers may be available that are
suitable.
the exit end of the column to the detector or turn on detector
gases during column conditioning.
7.4 Sample Headspace Vials, glass, 23 mL, with
11.2 Set the flow of detector gases as follows:
fluoropolymer-lined septa and aluminum caps.
Detector Gas Flow
7.5 Vial Sealer.
FID Hydrogen 30 to 40 cm /min
7.6 Analytical Balance, capable of weighing to 60.001 g.
Air 300 to 400 cm /min
7.7 Statistical Programmable Calculator.
PID Not required
HED Hydrogen 30 cm /min
NOTE 6—A programmable calculator is not absolutely necessary, but
11.3 Set other parameters as follows:
can save a considerable amount of time when large numbers of samples
are being analyzed.
11.3.1 Oven Temperature—50 to 60°C.
NOTE 9—Higher oven temperatures may be required when other
8. Reagents and Materials
chromatographic columns are used, or when high-boiling solvents and
8.1 Vinyl Chloride Monomer (neat), pure, preferably in
late-eluting materials are being driven from the column.
small cylinder.
11.3.2 Dosing Needle—150°C.
8.2 Standard Cylinders,vinylchloridemonomerinnitrogen
11.3.3 Injection Block Temperature—200°C.
at 1 and 10 ppm by volume.
11.3.4 Constant-Temperature Bath—90 6 1.0°C.
8.3 Hydrogen Cylinder, prepurified gas.
11.3.5 Carrier-Gas Flow Ra
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