10.2417/spepro.

005145

Measuring the concentration of

phthalate plasticizers in
poly(vinyl chloride)
Vadim V. Krongauz, Michael T. K. Ling, and John F. OConnell

A new gas chromatography method was used to analyze phthalate plasticizer concentration after poly(vinyl chloride) sample dissolution with
consequent phthalate extraction and polymer precipitation.
Poly(vinyl chloride) (PVC) became one of the most useful materials
known today after Waldo Lonsbury Semons discovery of plasticization in 1926. The use of plasticizers as such, however, began in the
mid-1860s when castor oil was added to soften cellulose nitrate.1, 2
Plasticized PVC is used in food packaging, shoes, furniture, cars, toys,
medical devices, clothing, plumbing, tool handles, and many other applications. The most popular plasticizer for PVC is di(2-ethylhexyl)
phthalate (DEHP). Like many other materials in consumer use, DEHP
was suspected as possibly causing adverse physiological effects.38 Although the debate over the existence of adverse DEHP effects continues, the analysis of DEHP and other phthalates present in PVC parts is
required by regulatory agencies. The concentration of tri(2-ethylhexyl)
trimellitate, di(2-ethylhexyl) terephthalate, and other plasticizers currently replacing DEHP in commercial products is also often examined.
To quantify the amount of phthalate plasticizers in PVC, analytical methods based on solvent extraction of phthalates from the polymer parts and consequent chromatographic analysis are employed.38
In many cases the solvent of choice does not dissolve PVC, and the
extraction only partitions the phthalate between the polymer part and
the solvent, leaving some amount of plasticizer remaining in the PVC.
Phthalate extraction from the PVC solid is time-consuming, since
molecular diffusion occurring during extraction from polymers is very
slow.912 To reduce measurement uncertainty, and to accelerate and
simplify the extraction of phthalate plasticizers from PVC, the US Consumer Product Safety Commission developed an analytical approach in
which an entire sample of plasticized PVC was used after dissolving it
in tetrahydrofuran (THF).8 The dissolved PVC was then precipitated
from THF by a nonpolar solvent (hexane), while phthalate plasticizers remained in the hexane/THF solution.8 Since PVC precipitation

Figure 1. Photographs of the consecutive steps in plasticized poly(vinyl

chloride) (PVC) analysis: 4.0g of methyl ethyl ketone was added to
plasticized PVC (left); 10.0ml of hexane was added in two steps (center); 5.0ml of 0.9% saline solution and 1.0g of sodium chloride were
added to precipitate the polymer and salt out the organic solvents from
the aqueous layer, followed by a 1h settling at 4C (right).

produced a stable PVC suspension, it was recommended that the

solution should be filtered.
We extended the method based on complete PVC dissolution8 by
eliminating the need for solution filtration.13 In our approach we also
dissolved plasticized PVC in a polar solvent, methyl ethyl ketone
(MEK), then precipitated PVC by adding a nonpolar solvent (hexane),
forming a PVC suspension. However, instead of filtration we broke the
PVC suspension and precipitated the PVC by adding an aqueous solution of a strong electrolyte such as sodium chloride. The electrolyte
cleanly precipitated and aggregated the PVC into a water-organic layer
interface (see Figure 1). The salting out effect described quantitatively
by Setschenow and Debye1417 ensured that MEK and hexane formed
an organic layer with a clean boundary where relatively nonpolar phthalate plasticizers were concentrated. The sample of organic layer was
then analyzed using our new gas chromatography (GC) procedure.13
Several gas chromatographic techniques were used for the analysis
of phthalates in the past.38 We developed another straightforward GC
method of phthalate analysis using a Supelcowax 10 capillary column,
designed for solute separation primarily based on molecule polarity.
After injection of the analyte solution, the column was held at 100C

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10.2417/spepro.005145 Page 2/3

for 5min, then the temperature was raised to 300C at 5C/min, and held
at 300C for 5min. Anisole was used as an internal standard. Our GC
method allowed simultaneous determination of high- and low-boiling
PVC formulation components13 (see Figure 2).
Poly(vinyl chloride) and other polymers may contain a variety of
additives, such as acid and radical scavengers, and antioxidants: for
example, 4-methoxy phenol (monomethyl hydroxyl quinone ester, or
MEHQ) and 3,5-di-tert-butyl-4-hydroxytoluene (butylhydroxytoluene,
or BHT). We used the Supelcowax 10 capillary column and the GC
conditions described above to demonstrate that our developed approach
would allow separation of stabilizers from each other and from the phthalate plasticizers (see Figure 3). The BHT and MEHQ separation discussed as an example of the capabilities of the GC analysis may require
less preparative work than the corresponding liquid chromatographic
methods.38
We successfully used our approach to find the phthalate plasticizer
concentration in a variety of plasticized PVC samples, such as pellets,
films, and finished parts, both developmental and commercial. We were
also able to quantify the organic stabilizers and radical scavenger additives present in some PVC samples. The extraction of plasticizers from
PVC by a solvent that does not dissolve PVC may be incomplete and is
definitely slow. Therefore, an approach based on complete dissolution
of the samples reduces the possibility of errors in quantitative analysis.
The precipitation of the PVC colloid using an aqueous electrolyte solution further improved the accuracy and precision of the method. Due
to its robustness, the method could be further modified and optimized

Figure 3. A typical chromatogram of the hexane solution of the stabilizers 3,5-di-tert-butyl-4-hydroxytoluene (butylhydroxytoluene, or BHT)
(tr 11.97min), and 4-methoxy phenol (monomethyl hydroxyl quinone
ester, or MEHQ) (tr 20.49min) obtained using a Supelcowax 10 capillary column with the GC method outlined in this article.
for different tasks, just as we modified the method first presented by
the scientists from the US Consumer Product Safety Commission. For
instance, the type and amount of solvent used to dissolve PVC samples
can be changed, or the thermal regime of the GC oven can be altered.
We would like to thank Baxter Healthcare Corporation for supporting
this work.

Author Information
Vadim V. Krongauz, Michael T. K. Ling, and John F. OConnell
Baxter Healthcare Corporation
Round Lake, IL
Vadim Krongauz is a senior research scientist. He has a BSc/MSc
in chemistry from the Lomonosov Moscow State University, Russia,
and a PhD in physical chemistry from the University of Washington,
Seattle.

Figure 2. A typical gas chromatogram (GC) of the hexane solution of the anisole internal standard (retention time (tr ) 1.6min),
di(2-ethylhexyl) phthalate (DEHP) (tr 32.77min), di(2-ethylhexyl)
terephthalate (DOTP) (tr 34.85min), and tri(2-ethylhexyl) trimellitate
(TOTM) (tr 43.75min) obtained using a Supelcowax 10 capillary column.

John OConnell is an engineer specialized in analytical chemistry. He

has a BSc in materials science and engineering (biomaterials) from the
University of Illinois, Champaign-Urbana.
Michael T. K. Ling is the senior director of the materials science division. He has an MSc in aerospace and mechanical engineering, and
an MEM from Northwestern University.
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10.2417/spepro.005145 Page 3/3

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c 2013 Society of Plastics Engineers (SPE)