ASTM D4747-02(2014)
(Test Method)Standard Test Method for Determining Unreacted Monomer Content of Latexes Using Gas-Liquid Chromatography (Withdrawn 2019)
Standard Test Method for Determining Unreacted Monomer Content of Latexes Using Gas-Liquid Chromatography (Withdrawn 2019)
SIGNIFICANCE AND USE
4.1 Excessive amounts of unreacted monomer may cause concerns relating to toxicity and odor. This test method is designed to measure the unreacted monomer content of latexes. The results may be used to monitor the extent of polymerization during manufacture, as well as to establish maximum unreacted monomer content for regulatory purposes.
SCOPE
1.1 This test method covers the determination of free monomer content of acrylic latexes. Monomers that have been successfully determined by this procedure include n-butyl methacrylate, n-butyl acrylate, styrene, and methyl methacrylate. The determination of other monomers has not been evaluated, but this test method is believed to be applicable. The established working range of this test method is from 100 to 1000 μg/g, but there is no reason to believe it will not work outside of this range, provided that appropriate dilutions and adjustments in specimen size are made.
1.2 The volatile composition of acrylic latexes is expected to change with time and environmental factors. This time dependence of the determination may be seen as an artificially large deviation of results, making the method mostly applicable for in-house quality control, where sampling and analysis conditions can be better controlled.
1.3 The values stated in inch-pound units are to be regarded as the standard. The values given in parentheses are for information only.
1.4 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. See Section 7 for specific hazard statements.
WITHDRAWN RATIONALE
This test method covers the determination of free monomer content of acrylic latexes. Monomers that have been successfully determined by this procedure include n-butyl methacrylate, n-butyl acrylate, styrene, and methyl methacrylate. The determination of other monomers has not been evaluated, but this test method is believed to be applicable. The established working range of this test method is from 100 to 1000 μg/g, but there is no reason to believe it will not work outside of this range, provided that appropriate dilutions and adjustments in specimen size are made.
Formerly under the jurisdiction of Committee D01 on Paint and Related Coatings, Materials, and Applications, this test method was withdrawn in December 2019 and replaced by D4827-2003(2015) Standard Test Method for Determining the Unreacted Monomer Content of Latexes Using Capillary Column Gas Chromatography1 because D4747 employs an outdated packed chromatography column and is being balloted for withdrawal. The standard will be replaced by D4827, which calls for an open-tubular capillary column.
General Information
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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
Designation: D4747 − 02 (Reapproved 2014)
Standard Test Method for
Determining Unreacted Monomer Content of Latexes Using
Gas-Liquid Chromatography
This standard is issued under the fixed designation D4747; 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 Related Materials (Withdrawn 1998)
E260 Practice for Packed Column Gas Chromatography
1.1 This test method covers the determination of free
monomer content of acrylic latexes. Monomers that have been
3. Summary of Test Method
successfully determined by this procedure include n-butyl
3.1 A suitable aliquot of the latex is internally standardized
methacrylate, n-butyl acrylate, styrene, and methyl methacry-
with isobutyl acrylate, diluted with water, and then injected
late. The determination of other monomers has not been
into a gas chromatographic column containing a packing
evaluated,butthistestmethodisbelievedtobeapplicable.The
material coated with a stationary phase that separates the
established working range of this test method is from 100 to
internal standard and monomers in question from each other
1000 µg/g, but there is no reason to believe it will not work
and from other volatile compounds.
outside of this range, provided that appropriate dilutions and
adjustments in specimen size are made.
4. Significance and Use
1.2 The volatile composition of acrylic latexes is expected
4.1 Excessive amounts of unreacted monomer may cause
to change with time and environmental factors. This time
concerns relating to toxicity and odor. This test method is
dependence of the determination may be seen as an artificially
designedtomeasuretheunreactedmonomercontentoflatexes.
large deviation of results, making the method mostly appli-
The results may be used to monitor the extent of polymeriza-
cableforin-housequalitycontrol,wheresamplingandanalysis
tion during manufacture, as well as to establish maximum
conditions can be better controlled.
unreacted monomer content for regulatory purposes.
1.3 The values stated in inch-pound units are to be regarded
5. Apparatus
as the standard. The values given in parentheses are for
5.1 Gas Chromatograph, any gas-liquid chromatographic
information only.
instrument having a flame ionization detector and linear
1.4 This standard does not purport to address all of the
temperature programming.An injection port using replaceable
safety concerns, if any, associated with its use. It is the
glass liners to facilitate periodic removal of accumulated
responsibility of the user of this standard to establish appro-
residues is recommended.
priate safety and health practices and determine the applica-
5.2 Column, 2 by 2-mm inside diameter glass or 6 ft by
bility of regulatory limitations prior to use. See Section 7 for
⁄8-in. outside diameter steel tubing, packed with 10 % by
specific hazard statements.
weight of a 2-nitroterephthalic acid derivative of a synthetic
polyester wax on 100/120 mesh acid washed, silane treated
2. Referenced Documents
diatomaceous earth. A column of equivalent or superior
2.1 ASTM Standards: performance may also be used.
D3980 Practice for Interlaboratory Testing of Paint and
5.3 Recorder—A recording potentiometer with a full-scale
deflection of 10 mV, a full-scale response time of 2 s or less,
and a maximum noise level of 60.03 % of full scale (see
This test method is under the jurisdiction of ASTM Committee D01 on Paint Practice E260).
and Related Coatings, Materials, andApplications and is the direct responsibility of
5.4 Liquid Charging Devices, microsyringe, 10-µL capacity
Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials.
Current edition approved July 1, 2014. Published July 2014. Originally approved or an automatic liquid sampling device.
in 1987. Last previous edition approved in 2008 as D4747 – 02 (2008). DOI:
10.1520/D4747-02R14.
2 3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or The last approved version of this historical standard is referenced on
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM www.astm.org.
Standards volume information, refer to the standard’s Document Summary page on Columns prepared from the stationary phases and supports have been found
the ASTM website. suitable for this purpose and are available from scientific supply houses.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4747 − 02 (2014)
5.5 Dropper Pipets, glass, disposable. skin or eye contact with these chemicals. All sample prepara-
tions should be done in a well-ventilated area, such as a fume
5.6 Vials,approximately7-mLcapacity,withcaps.Opentop
hood.
screw cap vials fitted with polytetrafluoroethylene/silicone
septa are preferred.
8. Preparation of Apparatus
5.7 Autosampler Vials, 2-mL capacity (optional).
8.1 Column Conditioning—Attach one end of the column to
5.8 Analytical Balance, accurate to 0.1 mg.
the inlet side of the instrument leaving the exit end of the
column disconnected. This prevents the contamination of the
detector due to column bleed. Set the helium flow rate at 30
TABLE 1 Instrument Conditions
mL/min and purge the column at ambient temperature for 30
Detector flame ionization min. Program the column oven from 50 to 220°C at 2°C/min
Air flow 240 mL/min
and maintain at 220°C overnight. In no case should the
Hydrogen flow 30 mL/min
temperature of the column be allowed to exceed 275°C.
Column (suggested) 2 by 2 mm inside diameter glass, packed with
10 % of a 2-nitroterephthalic acid derivative
8.2 Afterconditioning,connecttheexitendofthecolumnto
of Carbo-wax 20M on 100/120 mesh acid washed,
the detector and establish the operating conditions required to
silane-treated diatomaceous earth.
Carrier gas, flow rate Helium, 30 mL/min
give the desired separation (see Table 1).Allow sufficient time
Temperatures:
for the instrument to reach equilibrium as indicated by a stable
baseline. Control the detector temperature so that it is constant
Injection port 250°C
Detector block 250°C
to within 1°C without thermostat cycling which causes an
Column
uneven baseline. Adjust the carrier gas flow rate to a constant
value.
Initial 80°C
Hold time 4 min
Program rate 8°C/min
9. Calibration
Final 200°C, or higher as needed (see 8.1)
Final hold 10 min, or as needed 9.1 Determine the retention of each component expected to
Injection volume 2 µL
be present by injecting small amounts either separately or in
known mixtures. Retention times should be determined each
day the method is used.
9.2 Standardization—Determine in duplicate the relative
6. Reagents
response of the monomers of interest to the isobutyl acrylate
6.1 Purity of Reagents—Reagent grade chemicals shall be
internal standard as follows:
used in all tests. Unless otherwise indicated, it is intended that
9.2.1 Weigh to 0.1 mg about 0.05 g of isobutyl acrylate and
all reagents shall conform to the specifications of the Commit-
each monomer of interest into a vial (5.6). Weigh approxi-
tee onAnalytical Reagents of theAmerican Chemical Society,
mately5gof acetone into the vial and mix well.
where such specifications are available. Other grades may be
9.2.2 Weigh approximately 0.05 g of the solution (9.2.1)
used, provided it is first ascertained that the reagent is of
into another vial, add approximately5gof acetone and mix
sufficiently high purity to permit its use without lessening the
well.
accuracy of the determination.
9.2.3 Inject a 1-µL aliquot of the solution from 9.2.2 onto
thecolumnandrecordthechromatogram.Theelutionorderfor
6.2 Carrier Gas, helium of 99.995 % or higher purity. High
acetone and each of the monomers using the conditions given
purity nitrogen may also
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