Quantification of Plasticizers in Poly(vinyl chloride)

Commodities by High-Performance Thin-Layer

Chromatography
Elisabeth Dytkiewitz and Wolfgang Schwack*

Key Words
Plasticizer
High-performance thin-layer chromatography
PVC
ESBO
Phthalates

Summary Three phthalates (DEHP, BBP, and dibutyl phthalate [DBP])

Flexible packaging films, lids of glass jars, elastic toys, or medical
commodities made of poly(vinyl chloride) contain different plasti-
cizers, which tend to migrate out of the respective product. To test
compliance to regulations, the content of plasticizers and their
migration properties have to be determined analytically. With a
rapid high-performance thin-layer chromatography (HPTLC)
method it was able to quantify phthalic acid esters, diisononyl cyclo-
hexane-1,2-dicarboxylate, sebacates, citrates, adipates, and epoxi-
dized soybean oil (ESBO) simultaneously. Chromatography was
performed on HPTLC silica gel glass plates, and detection was
enabled by dipping the plate into primuline solution. ESBO could be
quantified after a newly introduced lipase treatment and chro-
matography of the epoxidized fatty acids. Validation was performed
by analyzing self-made plastisols, showing good recoveries and stan-
dard deviations. Limits of detection and quantification generally
were approximately 10–20 and 30–60 ng per zone, respectively, but
the detection of ESBO required 70 ng per zone. Thus, plasticizers in
PVC samples could be quantified even if they were present as cont-
amination at low concentrations.
1 Introduction
Plasticizers are common additives to produce plastic materials
of flexible properties, especially the case for commodities made
from poly(vinyl chloride) (PVC). To achieve flexible packaging
films (cling films), elastic toys, lid gaskets, or medical tubes up
to 50% or even more, plasticizers are added to PVC [1–3].
Phthalic acid esters (PAE) are an important group of plasticizers,
but their impact on human health is still under discussion. The
European Food Safety Authority (EFSA) published opinions
concerning the tolerable daily intake (TDI) of different phtha-
lates set by the Scientific Committee for Food (SCF) and the
exposure by food contact material. Thereby, the TDI of diisode-
cyl phthalate (DIDP) (0.15 mg kg–1) [4], bis(2-ethylhexyl)
phthalate (DEHP) (0.05 mg kg–1) [5], and butyl benzyl phthalate
(BBP) (0.1 mg kg–1) [6] was discussed.
E. Dytkiewitz and W. Schwack, University of Hohenheim, Institute of Food
Chemistry, Garbenstraße 28, D-70599 Stuttgart, Germany.
E-mail: wolfgang.schwack@uni-hohenheim.de
were generally banned for the use in toys and childcare prod-
ucts, implying that their content must be below 0.1%. This also
holds true for DIDP, diisononyl phthalate (DINP), and di-n-octyl
phthalate (DNOP) if the articles can be taken into the mouth of
children [7]. For plastic material intended to come into contact
with food, specific migration limits of phthalates have been
fixed by the European Commission, ranging between 0.3 and
30 mg kg–1 food [8].
During the last years, the so-called alternative plasticizers were
established, claiming lower risk to human health. Examples are
diisononyl cyclohexane-1,2-dicarboxylate (DINCH), adipates
like dioctyl adipate (DOA), sebacates like dibutyl sebacate
(DBS), citrates like acetyl tributyl citrate (ATBC), and epoxi-
dized soybean oil (ESBO). For these non-phthalates, specific
migration limits were set ranging between 16 and 60 mg kg–1
food [8]. To control good manufacturing practices or migration
into solvents used as food simulants, suitable methods of analy-
sis are required. The content of plasticizers in PVC samples can
already give an idea on potential migration into food and
exceeding migration limits. Considering the different chemical
properties of the used plasticizers, different analytical methods
are required to analyze them. Additives of low molecular weight
are commonly determined by gas chromatography with flame
ionization detection (GC-FID) [9, 10] or mass selective detec-
tion (GC–MS) [11, 12]. For the determination of high molecular
ESBO in packaging material, GC–MS methods requiring trans-
methylation were introduced [13, 14]. A rapid screening for the
presence of different types of plasticizers in PVC materials was
shown by direct analysis in real time-mass spectrometry
(DART-MS) [15, 16]. Planar chromatography was only applied
in few cases, especially for the determination of some PAE.
With special attention on toys, DIDP and DINP were analyzed
on RP-8 plates with a mobile phase consisting of acetonitrile,
tetrahydrofuran, and water because high-performance liquid
chromatography (HPLC) did not result in sharp peaks for these
two plasticizers [17]. Silica gel plates and n-hexane–acetone as
mobile phase were used for the determination of DBP, diethyl
phthalate (DEP), dimethyl phthalate (DMP), and diisooctyl
phthalate in surface water [18]. A third work introduced a com-
bination of n-hexane, toluene, and ethyl acetate as mobile phase

238 Journal of Planar Chromatography 25 (2012) 3, 238–243

0933-4173/$ 20.00 © Akadémiai Kiadó, Budapest
DOI: 10.1556/JPC.25.2012.3.9