New Approach to Analysis

of Formaldehyde in Water
Soluble Polymers
Application Note
By: Glynda Smith, Tekmar-Dohrmann
Vincent W. Hesler, Rohm and Haas Company

Abstract
Water-soluble polymers are widely used as chemical coatings. Often these coatings are exposed to high
temperatures during the drying of the product, releasing unbound volatile organics. Such releases must be
avoided, as they pose industrial hygiene issues. By correctly determining the evolved formaldehyde in the
coatings, the material can be assessed as either acceptable or unacceptable batches. Currently, ASTM Method
D5910 is the standard method for the analysis of free formaldehyde in emulsion polymers. The method is lengthy
and requires the use of a post-column reactor. In this paper, the potential for a simple quality control method is
explored using static headspace with analysis by gas chromatography.

Introduction
The amount of formaldehyde released during the drying and curing of a latex binder is the sum of the free
formaldehyde present in the latex and the formaldehyde released during heating as a result of the crosslinking
chemistry. Static headspace sampling is an easily automated approach to analyzing volatile materials. In this
technique, a sample is heated in a closed system, and the volatile components move into the vapor phase until
equilibrium is established. A sample of the headspace gas is then removed and analyzed. The technique has
been used qualitatively for many different types of polymeric materials, but quantitation can be difficult because
the extent to which a volatile partitions between the sample and the vapor phase is generally not known.
However, if static headspace sampling is used in a pseudo-dynamic, full-evaporation mode, quantitation is much
easier. By keeping the sample-to-headspace volume low, the samples can essentially be dried and the
formaldehyde released can be measured without the thermodynamic limitations that would otherwise be of
concern.
In the method described, the headspace gas is automatically sampled into a gas chromatograph where
formaldehyde is separated from other volatiles and detected with a mass selective detector. The system is easily
automated, does not require derivatization or trapping techniques, and is very selective for formaldehyde.

Experimental
The method uses a full evaporation technique of a very small sample (20 L) that is equilibrated at 150C for a
specified curing time. An aliquot of the headspace is transferred via a heated transfer line into a gas
chromatograph equipped with a mass selective detector (MSD) which is operated in the single ion mode for
optimum sensitivity. Cyclopropyl methyl ketone (CPMK) is used as an internal standard. The m/z 29 is used to
determine that the quantified peak is formaldehyde; the ratio of the m/z 30 of formaldehyde to the m/z 84 of
CPMK is used for quantitation.
Standards were prepared at concentrations ranging from approximately 200 to 10,000 ppm formaldehyde by
weight. A stock 1000 ppm solution of the CPMK internal standard was also prepared . A mixture containing 1.00
g. internal standard stock solution and 1.00 g. of standard was prepared, shaken thoroughly, and 20 L was
pipetted into two headspace vials. This procedure was repeated for each standard. Duplicate standards in order
of increasing concentration were analyzed followed by an internal standard blank (1.00 g. water + 1.00 g. internal
standard solution). Polymer emulsion samples were prepared for analysis in the same manner as the standards
using 1.00 g. of the as received sample.

7000-012.doc; 10-Jun-03

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Tekmar 7000/7050 HT Static Headspace Analyzer Conditions

Headspace vial volume:

22 mL

Loop fill time:

Sample temperature:

150C

Inject time:

0.20 min.
1.0 min.

Sample equilibration time:

30 minutes

Loop temperature:

190C

Vial pressurization:

20 psi

Transfer line temperature:

200C

Pressurization time:

0.5 min.

Injections per vial:

Sample loop volume:

1 mL

Hewlett Packard 5890 GC/5971A Mass Spectrometer

Column:

J & W Scientific DB-Wax 30 m x 0.25 mm x 0.50 um

Injection port temperature:

225C

Temperature program:

40C (hold for three minutes). Increase temperature

by 20C per minute to a final temperature of 230C.

Helium carrier flow:

33 cm/sec

Split ratio:

1:30

MSD acquisition:

29, 30 m/z - Group 1. 84 m/z - Group 2

Dwell time:

100 ms

Results
Duplicate standards in order of increasing concentration were analyzed using the conditions described in the
experimental section. Following the analysis of the standards, single ion chromatograms were integrated for m/z
30 for formaldehyde and m/z 84 for the internal standard. The formaldehyde peak elutes just after the air peak,
and is baseline resolved as seen in Figures 1-3 for the 200 ppm, 500 ppm and 1000 ppm formaldehyde
standards, respectively. The standard MSD autotune was used in obtaining the chromatograms in Figures 1-3.
However, by using maximum sensitivity autotune on the MSD, the formaldehyde sensitivity increases nearly
sevenfold without compromising reproducibility or the dynamic linear working range of the method. Figure 4
shows the effect of using maximum sensitivity autotune with the 200 ppm formaldehyde standard. The polymer
emulsion samples were analyzed as received with the addition of internal standard solution. Figure 5 shows the
chromatogram obtained for a typical Rohm and Haas polymer emulsion sample. The formaldehyde released from
the sample is clearly resolved from the air peak and no matrix modifications were necessary to enhance the
response. Calibration of the static headspace system was linear as shown in Figure 6. The method appears to
be viable over a wide range of formaldehyde concentrations. Nevertheless, if the samples under analysis are
likely to have very different formaldehyde levels, it is recommended to use a log*log least squares regression or to
compute several regression lines each covering a different range of concentrations.

Conclusions
Static headspace sampling can be used to predict the amount of formaldehyde released from a latex binder
during drying and curing. Absolute comparisons to levels generated during production are difficult because of
possible variations in temperature and curing time. Nevertheless, the method can provide information on
maximum formaldehyde levels and on relative formaldehyde levels for product comparisons that cannot be
derived from free formaldehyde data.

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