ASTM D5910-96

Standard Test Method for Determination of Free Formaldehyde in Emulsion Polymers by Liquid Chromatography (Withdrawn 2005)

SCOPE
1.1 This test method is used for the determination of free formaldehyde (HCHO) in emulsion polymers without upsetting existing formaldehyde equilibria. The procedure has been evaluated using acrylic, acrylonitrile-butadiene, carboxylated styrene-butadiene and polyvinyl acetate emulsion polymers. This test method may also be applicable for emulsion polymers of other compositions. The established working range of this test method is from 0.05 to 15 ppm formaldehyde. Emulsion polymers must be diluted to meet the working range.  
1.2 This test method minimizes changes in free formaldehyde concentration that can result from changes in the physical or chemical properties of an emulsion polymer.  
1.3 There are no known limitations to this test method when used in the manner described. The emulsion polymer test specimen must be prepared with a diluent that has a pH similar to that of the emulsion. Use of an inappropriate pH may upset formaldehyde equilibria and result in incorrect formaldehyde levels.  
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.
WITHDRAWN RATIONALE
This test method is used for the determination of free formaldehyde (HCHO) in emulsion polymers without upsetting existing formaldehyde equilibria. The procedure has been evaluated using acrylic, acrylonitrile-butadiene, carboxylated styrene-butadiene and polyvinyl acetate emulsion polymers. This test method may also be applicable for emulsion polymers of other compositions. The established working range of this test method is from 0.05 to 15 ppm formaldehyde. Emulsion polymers must be diluted to meet the working range.
Formerly under the jurisdiction of Committee D01 on Paint and Related Coatings, Materials, and Applications, this test method was withdrawn in December 2004 in accordance with section 10.6.3.1 of the Regulations Governing ASTM Technical Committees, which requires that standards shall be updated by the end of the eighth year since the last approval date.

General Information

• Status: Historical
• Publication Date: 31-Dec-1995
• Withdrawal Date: 21-Mar-2005
• ICS: 71.040.50 - Physicochemical methods of analysis
• Technical Committee: D01 - Paint and Related Coatings, Materials, and Applications
• Drafting Committee: D01.33 - Polymers and Resins

Relations

• Replaced By: ASTM D5910-05 - Standard Test Method for Determination of Free Formaldehyde in Emulsion Polymers by Liquid Chromatography
• Effective Date: 01-Oct-2005

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:D5910–96
Standard Test Method for
Determination of Free Formaldehyde in Emulsion Polymers
by Liquid Chromatography
This standard is issued under the fixed designation D 5910; 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.
1. Scope E 682 Practice for Liquid Chromatography Terms and Re-
lationships
1.1 This test method is used for the determination of free
formaldehyde (HCHO) in emulsion polymers without upset-
3. Summary of Test Method
ting existing formaldehyde equilibria. The procedure has been
3.1 The aqueous phase of an emulsion polymer is diluted
evaluated using acrylic, acrylonitrile-butadiene, carboxylated
and chromatographed on a reversed-phase octadecyl silane
styrene-butadiene and polyvinyl acetate emulsion polymers.
(ODS) column using an aqueous mobile phase and a visible-
Thistestmethodmayalsobeapplicableforemulsionpolymers
light detector at 410 nm. Formaldehyde is separated from other
of other compositions. The established working range of this
species in the matrix on a chromatographic column. The
test method is from 0.05 to 15 ppm formaldehyde. Emulsion
detection system includes a post-column reactor that produces
polymers must be diluted to meet the working range.
a lutidine derivative when formaldehyde reacts with the
1.2 This test method minimizes changes in free formalde-
2,4-pentanedione reagent (Nash Reagent). The concentration
hyde concentration that can result from changes in the physical
offreeformaldehydeinemulsionpolymersisdeterminedusing
or chemical properties of an emulsion polymer.
peak areas from the standard and sample chromatograms. This
1.3 There are no known limitations to this test method when
test method is specific for formaldehyde.
used in the manner described. The emulsion polymer test
specimen must be prepared with a diluent that has a pH similar
4. Significance and Use
to that of the emulsion. Use of an inappropriate pH may upset
4.1 With the need to calculate free formaldehyde levels in
formaldehyde equilibria and result in incorrect formaldehyde
emulsion polymers, it is necessary to make the determination
levels.
without upsetting any equilibria that might generate or deplete
1.4 This standard does not purport to address all of the
formaldehyde. This test method provides a means for deter-
safety concerns, if any, associated with its use. It is the
mining ppm levels of free formaldehyde in emulsion polymers
responsibility of the user of this standard to establish appro-
without upsetting existing equilibria.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use.
5. Interferences
5.1 This test method is very selective for formaldehyde.
2. Referenced Documents
Potential interferants are either chromatographically separated
2.1 ASTM Standards:
from formaldehyde or do not react with the post-column
D 1193 Specification for Reagent Water
reagent.
D 2194 Test Method for Concentration of Formaldehyde
Solutions
NOTE 1—The following species were identified as possible interfer-
ences for the method: acetaldehyde, acetone, benzaldehyde, formamide,
E 180 Practice for Determining the Precision of ASTM
formic acid, glyoxylic acid and propionaldehyde. These species, when
Methods forAnalysis and Testing of Industrial Chemicals
chromatographed using this test method, did not interfere with the
formaldehyde peak at the 1000 ppm level or lower.
This test method is under the jurisdiction of ASTM Committee D-1 on Paint
5.2 Because emulsion polymers vary in composition, the
and Related Coatings, Materials, andApplications and is the direct responsibility of
method run time may need to be extended to allow for late
Subcommittee D01.33 on Polymers and Resins.
Current edition approved Feb. 10, 1996. Published April 1996.
Annual Book of ASTM Standards, Vol 11.01.
Annual Book of ASTM Standards, Vol 06.04.
4 5
Annual Book of ASTM Standards, Vol 15.05. Annual Book of ASTM Standards, Vol 14.01.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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.
D5910–96
eluting compounds. Compounds that remain on the column 8. Configuration of Post-Column Reactor (PCR)
after an analysis may interfere with the formaldehyde peak in
8.1 The post-column reagent passes through a pulsedamp-
subsequent runs. 13 12
ener and an in-line check valve prior to the mixing tee.The
outlet of the analytical column is connected to one side of a
6. Apparatus
mixing tee. The reaction coil is connected to the outlet of the
6.1 Liquid Chromatograph—Any liquid chromatographic mixing tee. Stainless steel tubing with 0.25-mm inside diam-
eter is used to make the connections. Tubing lengths should be
instrument having an injection valve, a post-column reactor, a
410-nm UV-Vis detector, and an isocratic solvent delivery kepttoaminimum.Themixingteeandreactioncoilareplaced
inside a 95°C oven. A 40 cm-length of 0.25-mm inside
system may be used. The solvent delivery system must deliver
a mobile phase flow of 0.6 mL/min. diameter stainless steel tubing is connected to the outlet of the
reaction coil and is placed in an ambient-temperature stirred
NOTE 2—The UV-Vis detector may incorporate either a tungsten lamp
water bath. (This configuration acts as a heat exchanger.) The
or a deuterium lamp with a second order visible filter that filters out light
exit of the stainless steel tubing is connected to the UV/Vis
below 400 nm.
detector. Fig. 1 shows a schematic of the system.
6.2 Post-Column Reactor—Any post-column reactor that
can deliver a reagent flow at 0.5 mL/min, contains a Knitted
Reaction Coil that can be heated to 95°C and contains a static
,
7 8
mixing tee.
6.3 Chromatographic Column—Column should be 250 by
4.6 mm inside diameter packed with a reversed-phase pH
stable C18, 5-µm particles.
6.4 Chromatographic Guard Column—The column should
be 10 by 4.6 mm inside diameter packed with a reversed-phase
pH stable C18 5-µm particles.
6.5 Data System, that can collect data at 1 point/s from a
1-V output detector.
6.6 Syringe—100 µL capacity.
6.7 Sample Filter—The filter should consist of a 5-mL
sample syringe and a 0.1-µm-filter assembly to remove micro
particulate matter from the prepared sample solution.
6.8 Centrifuge—Any high speed centrifuge that can gener-
ate 50 000 r/min (274 980 g) or greater (Procedure 2).
6.9 Centrifuge—Any centrifuge that can generate 1000
r/min or greater (Procedure 3).
7. Configuration of Liquid Chromatograph
7.1 An in-line check valve is placed between the pump
and the injector. The guard and analytical columns are con-
nected to the injector. The outlet of the analytical column is
connected to the mixing tee as described in 8.1.
Knitted capillary delay tube such as Supelco No. 5-9206 available from
Supelco Inc., Supelco Park, Bellefonte, PA 16823 has been found satisfactory for
this purpose.
Staticmixingtee,availablefromUpchurchScientific,619W.OakSt.,P.O.Box
1529, Oak Harbor, WA 98277-1529, Catalog No. U-466, has been found to be
satisfactory for this purpose.
Timberline RDR-1, available from Alltech Associates, Inc., 2051 Waukegan
Rd., Deerfield, IL 60015, with two 0.4-mL serpentine reaction coils in series, has
FIG. 1 Schematic of Liquid Chromatograph and Post-Column
been found to be satisfactory for this purpose.
Reaction Systems
Commercial analytical columns that have been found to be satisfactory for use
during round-robin evaluation include: Phase Separations, Inc., 140 Water St.,
Norwalk, CT 06854, pH Stable C18, Catalog No. 838715 and Alltech Associates,
9. Reagents and Materials
Inc., Spherisorb pH Stable C18 Sil 5U, Catalog No. 82055.
Commercial guard columns that have found to be satisfactory for use during
9.1 Purity of Reagents—Reagent grade chemicals shall be
round-robin evaluation include:AlltechAssociates, Inc., Spherisorb pH Stable C18
used with this test method. Unless otherwise indicated, it is
Sil 5U, Catalog No. C-8800.
Filter such as Anotop 25 Plus Syringe Filter, 0.1 µm, Catalog No. 2270,
available from Alltech Assoc., has been found to be satisfactory for this purpose.
12 13
In-line check valve CV-3001 and U-469, Catalog No. 2270, from Upchurch Pulse dampener, SSI LO, Catalog No. 20-0218, available fromAlltechAssoc.,
Scientific has been found to be satisfactory for this purpose. has been found to be satisfactory for this purpose.
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.
D5910–96
intended that all reagents shall conform to the specification of 10.2.1 Transfer1.78gofsodiumphosphate,dibasictoa2-L
theCommitteeonAnalyticalReagentsoftheAmericanChemi- mobilephasereservoirthatcontainsastirbar.Add2Lofwater
cal Society, where such specifications are available. Other and mix on a stir plate until the sodium phosphate, dibasic has
grades may be used, provided it is first ascertained that the completely dissolved.
reagent is of sufficiently high purity to permit its use without
10.2.2 Adjust the pH of the solution to 7.0 with 0.1 N
lessening the accuracy of the determination. phosphoric acid.
9.2 Water—Unless otherwise indicated, references to water 10.2.3 Degas the mobile phase with a helium sparge.
shall be understood to mean reagent water minimally conform-
NOTE 5—Water may also be used as the mobile phase without the
ing to Type II of Specification D 1193, or distilled deionized
addition of a buffer.Awater mobile phase should be used when the Carrez
water. High-performance liquid chromatography (HPLC)
reagents are used in the sample preparation (see section 12.2.3).
grade water from chromatography suppliers is also acceptable.
10.3 Sample Diluent:
9.3 Acetic Acid, glacial (CH CO H).
3 2
10.3.1 Transfer0.89gofsodiumphosphate,dibasictoa1-L
9.4 Ammonium Acetate—(CH CO NH ).
3 2 4
bottle that contains a stir bar. Add 1 L of water and mix on a
9.5 Formaldehyde, 37 % (HCHO).
stir plate until the sodium phosphate, dibasic has completely
9.6 2,4-Pentanedione, 99 % (CH COCH COCH ).
3 2 3
dissolved.
9.7 Phosphoric Acid Solution (0.1 N)— Dissolve 2.3 mL of
10.3.2 ThefinalstepofthediluentpreparationrequiresapH
phosphoric acid 85 % (H PO ) in water and dilute to 1 L with
3 4
adjustment. Before that step can occur the pH of the emulsion
water.
polymers must be measured to 0.1 pH unit. The emulsion
9.8 Potassium Ferrocyanide Trihydrate Solution (36 g/L)
polymers must be diluted with a buffer that is 60.1 pH unit of
[Carrez Solution I]—Dissolve 26 g of potassium ferrocyanide
the emulsion polymer.
trihydrate, 99 % (K Fe(CN) ·3H O) in water and dilute to 1 L
4 6 2
10.3.3 Divide the 1-L solution into the number of separate
with water.
diluents required as mentioned in 10.3.2.
9.9 Zinc Sulfate Heptahydrate (72 g/L) [Carrez Solution
10.3.4 Adjust the pH of the diluents to 0.1 pH unit using
II]—Dissolve 72 g of zinc sulfate heptahydrate, 99.9 %
either 0.1 N NaOH or 0.1 N H PO .
3 4
(ZnSO ·7H O) in water and dilute to 1 L with water.
4 2
9.10 Sodium Hydroxide (0.1 N)—Dissolve8gof sodium
11. Operating Conditions for Analysis
hydroxide 50 % (NaOH) in water and dilute to 1 L with water.
11.1 Adjust the liquid chromatograph in accordance with
9.11 Sodium Phosphate, dibasic, 98 % (Na HPO ).
2 4
the manufacturers’ directions and the following parameters.
Allow the instrument to equilibrate until a stable base line is
10. Preparation
obtained on the data system.
10.1 Post-Column Reagent (Nash Reagent):
Column temperature: ambient
10.1.1 Transfer 62.5 g of ammonium acetate to a 1-Lamber
Mobile phase: 6.3 mM Na HPO (pH = 7) or water
2 4
Flow rate: 0.6 mL/min
bottle that contains a stir bar. Add 600 mL of water to the
Injection volume: 50 µL
bottle and mix on a stir plate until the ammonium acetate has
PCR temperature: 95°C
completed dissolved.
PCR flow rate: 0.5 mL/min
Detector: UV/Vis, 410 nm
10.1.2 Pipet 7.5 mL of glacial acetic acid into the bottle.
Pipet 5 mL of 2,4-pentanedione into the bottle. Add 387.5 mL
11.2 Determine whether the system is working properly by
of water to the bottle and mix thoroughly (45 min of mixing is
injecting 50 µLof a 10 ppm formaldehyde standard solution.A
suggested).
typical chromatogram of a 10-ppm formaldehyde standard
obtained under the conditions outlined in 11.1 is shown in Fig.
NOTE 3—2,4-Pentanedione is light sensitive and should be protected
2. Make sure that the peak asymmetry (A at 10 % peak height)
from light during use. s
value for formaldehyde is within the range of 0.8 and 1.7.
NOTE 4—The post-column reagent should be prepared weekly.
Determination of peak asymmetry should be performed in
10.1.3 Transfer the post-column reagent to the post-column
accordance with Practice E 682. A typical retention time for
reactor reservoir. The reservoir should be protected from light.
formaldehyde is 6 min.
10.1.4 Degas the post-column reagent with a helium sparge.
11.3 The run time for the analysis is 10 min. The run time
10.2 Mobile Phase and Standard Diluent:
may have to be extended 20 to 30 min if late eluting
compoundsinterferewiththeformaldehydepeakinsubsequent
runs.
Reagent Chemicals, American Chemical Society Specifications, American
12. Calibration and Standardization
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
12.1 Prepare a 25-mLstock solution of formaldehyde at the
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
1.18 % (11 840 ppm) level by adding 0.8 g of formaldehyde
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
(37 %) to 24.2 g standard diluent.
MD.
2,4-Pentanedione (acetyl acetone), 99 %, available from Aldrich Chemical
NOTE 6—Reagent grade formaldehyde is nominally 37 %. Perform the
Co., 2905 W. Hope Ave., Milwaukee, WI 53216, Catalog No. P775-4, has been
assay of the formaldehyde solution in accordance with Test Method
found to be satisfactory for this method.
A bottle that filters out ultraviolet and visible light is suitable. D 2194.
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn. Contact ASTM
International (www.astm.org) f
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