Reactive and Functional Polymers 113 (2017) 70–76

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Reactive and Functional Polymers

journal homepage: www.elsevier.com/locate/react

Evaluation of the temperature and molecular weight dependent

migration of di(2-ethylhexyl) phthalate from isotactic
polypropylene composites
Adhimoorthy Prasannan a, Jheng-Jun Jhu a, Chih-Jen Wu b,c, Shuian-Yin Lin d, Hsieh-Chih Tsai a,⁎
a
Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei 106, Taiwan, ROC
b
Division of Nephrology, Department of Internal Medicine, Mackay Memorial Hospital, Taipei, Taiwan, ROC
c
Graduate Institute of Medical Science, Taipei Medical University, Taipei, Taiwan, ROC
d
National Applied Research Laboratories, Instrument Technology Research Center, Hsinchu, Taiwan, ROC

a r t i c l e i n f o a b s t r a c t

Article history: The development of a process for the bioremediation of di(2-ethylhexyl) phthalate (DEHP) blended in various
Received 15 July 2016 polymers, with a low DEHP release rate, has become an essential mission in the packaging materials industry, es-
Received in revised form 9 February 2017 pecially for blood-component storage materials. Hence, polypropylene and DEHP composites were prepared to
Accepted 12 February 2017
evaluate their DEHP release behavior at 90 °C and 25 °C. The physical and chemical properties of the composites
Available online 14 February 2017
were evaluated with various analytical tools. Polypropylene of three different molecular weights was used to
Keywords:
compare the different DEHP releasing rates. The incorporation and migration of DEHP significantly followed
DEHP migration the crystalline nature of the polymer matrix. The temperature-dependent migration behavior was evaluated
Polymer composites by UV–Vis spectroscopy and LC/MS analyses. Among the three different molecular weight PP/DEHP composites,
Polypropylene a significantly lower amount of DEHP was released from the higher molecular weight polymer composite due to
Crystallization its enriched crystalline nature. Moreover, the release behavior of DEHP was affected by the molecular weight and
Molecular weight crystalline nature of PP, which can strongly hold the plasticizer, and therefore slow down its release. The high
molecular weight iPP/DEHP composite may be suitable for blood-component backing materials because of its
lower DEHP migration.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction toxicities. Consequently, minimizing the use of PVC would result in a

In the packaging industry, the use of active packaging materials is an
effective approach to sustain the quality of products during prolonged
shelf times; the ecological interaction, or improved safety [1]. Therefore,
although a variety of active packaging strategies have been demonstrat-
ed to be of affordable quality, wholesome, and safe, their application has
been limited due to their package-related environmental pollution and
disposal problems [2]. For example, the packaging materials used in dis-
posable blood bags are used for the collection, storage, transportation,
and transfusion of human blood and blood components. In this regard,
plasticized poly(vinyl chloride) (PVC) is one of the most widely used
materials in blood bags, however it does not have good handling charac-
teristics, and lacks indispensable properties for the survival of red blood
cells [3]. In addition, most PVC-containing medical products slowly lib-
erate free chlorine, chlorine species (including phosgene), and dioxins,
all of which are associated with carcinogenicity and other potential
⁎ Corresponding author.
E-mail address: h.c.tsai@mail.ntust.edu.tw (H.-C. Tsai).
lower exposure to potential toxicities.
Research into the fabrication of single-use packaging materials that
do not elute offensive effluents for medical applications has become
an emerging field for health-care storage applications. Some ther-
moplastic elastomers (TPE) that have been most commonly used
as substitutes of PVC include ethylvinylacetate (EVA), polyolefins,
polyurethanes (PU), and fluoropolymers [4]. However, most of
these plastics are not effective for the preparation of proficient pack-
aging materials, and therefore required other additives such as plas-
ticizers, antioxidants, or stabilizers to improve their properties
without additional risks [5].
In order to produce plastics with a desired flexibility, plasticizers
have long been used in various fields ranging from the automotive in-
dustry to health-care and consumer products [6]. Di-(2-ethylhexyl)
phthalate (DEHP) was reported to be the most used plasticizer in PVC
to endow it with flexibility [7]. However, leached DEHP was found in
PVC/DEHP containers, causing toxic effects in humans. DEHP can easily
enter the body through different pathways such as the skin, intestine,
and other tissues due to their lipophilic nature [8]. The introduction of
DEHP in the human body may cause cancer and generate endocrine

http://dx.doi.org/10.1016/j.reactfunctpolym.2017.02.007
1381-5148/© 2017 Elsevier B.V. All rights reserved.
 A. Prasannan et al. / Reactive and Functional Polymers 113 (2017) 70–76 71

Fig. 1. Migration assay of DEHP and its hydrolysis process.

effects, particularly in young males. In order to avoid DEHP consump- at two different temperatures (25 °C and 90 °C). As mentioned in
tion, various methods have been applied to produce an appropriate Fig. 1, the DEHP extractions occurred through the hydrolysis of DEHP.
DEHP substitute in blood components bags [9–10]. In this respect, the
selection of an appropriate polymer matrix may be an important factor 2.4. Characterization
for reducing the migration of DEHP active agents. The development of a
semi-crystalline polymer matrix based on new composite materials Fourier transform infrared (FTIR) spectra of the composites were re-
may be suitable for the reduction of the active agents. In this regard, corded on a Nicolet 6700 (Thermo Scientific) FT-IR spectrometer. The
polypropylene (PP) is an ideal material due to its chemically resistant morphology of the composites was characterized using an FE-SEM
nature, excellent mechanical properties, and easy processing. Hence, with a JSM 6330F (JEOL). The PP/DEHP composite was characterized
DEHP embedded in a PP matrix could minimize DEHP leaching due to by wide-angle X-ray diffraction (WAXD) with a Bruker AXS D2 Phaser
the structure of the composite, and therefore could improve the me- type X-ray diffractometer. A Perkin Elmer Pyris differential scanning cal-
chanical and barrier properties of the polymer matrix. orimeter, equipped with an intra-cooler, was used to determine the
In this study, a novel PP/DEHP composite was synthesized to evalu- melting and crystallization temperature of the PP/DEHP blend. Further-
ate the migration behavior of DEHP from a polymer composite matrix. more, a Jasco V-670 Ultraviolet-Visible spectrometer was used to evalu-
In order to evaluate the DEHP migration, three different molecular ate the DEHP migration assay.
weights of PP were used at two different temperatures, and they were
compared through the influence of their crystalline domains. The mi-
gration of DEHP was affected by the molecular weight and crystalline
nature of PP. Furthermore, the physical properties of the blend can be
improve blood-component bag materials through their degree of crys-
tallinity and controlled DEHP migration, which may play a vital role in
blood compatibility.

2. Experimental

2.1. Materials

Polypropylene with various molecular weights such as amorphous

polypropylene (aPP) with an average Mw of ~ 14,000 and an average
Mn of ~ 3700; isotactic polypropylene (iPP12) with an average
Mw ~ 12,000 and an average Mn ~ 5000; and isotactic polypropylene
(iPP250) with an average Mw ~ 250,000 and average Mn ~ 67,000
were purchased from Sigma-Aldrich, Taiwan. Di(2-ethylhexyl) phthal-
ate (DEHP) was purchased from Acros-Organics, Taiwan.

2.2. PP/DEHP blend

In order to prepare the PP/DEHP composites, a calculated amount of

DEHP was introduced into the PP matrix using a melt blend. First, DEHP
was added to PP to a concentration of 30% (w/w), and then the PP/DEHP
blend was mixed by melt blending at 180 °C for 8 h. The melt-blended
samples were cooled to room temperature for further experiments.

2.3. DEHP migration assay design

To evaluate the DEHP migration analysis, the PP/DEHP blended sam-

ples were added to an aqueous solution, and then they were extracted Fig. 2. FT-IR spectroscopy evidence for iPP/DEHP composites.
72 A. Prasannan et al. / Reactive and Functional Polymers 113 (2017) 70–76

Table 1 relationship between DEHP loading and the structure and morphology
Comparison of crystalline portion from FT-IR and DSC methods. of the PP crystals.
Material A998/A973a Degree of crystallinityb % FT-IR was used to understand the chemical composition of the PP/
iPP250 (isotactic, Mw ~ 250,000) 0.959 30.4
DEHP composites. As shown in Fig. 2, three major regions were exhibit-
iPP12 (isotactic, Mw ~ 12,000) 0.323 1.4 ed, with one of these regions located at 2800–3000 cm−1. The broad ab-
aPP(amorphous, Mw ~ 14,000) 0.251 4.7 sorption peaks at around 2953 cm−1 were assigned to the CH2 and CH3
iPP250 (isotactic, Mw ~ 250,000)/DEHP 0.884 1.8 asymmetric and symmetric vibrations of PP. In the second region, the
iPP12 (isotactic, Mw ~ 12,000)/DEHP 0.230 0.8
peaks at 1376 cm− 1 and 1455 cm− 1 were attributed to the CH2 and
aPP(amorphous, Mw ~ 14,000)/DEHP 0.242 1.6
CH3 deformation vibrations of the aliphatic group in the polymer chains
a
Calculated from the FTIR. [12]. The CH3 symmetric bending vibration peak was identified at
b
Calculated from the DSC [Degree of crystallinity = [(Delta Hf − Delta Hc) / Delta
Hf O) × 100%].
around 1160 cm−1, which can vary based on the molecular size and
three-dimensional structure of PP [13]. The additional carbonyl
stretching vibration at 1747 cm−1, in the third region, was attributed
3. Results and discussion to DEHP [14].
To facilitate the effect of DEHP on the crystalline nature of the PP ma-
3.1. Structural evaluation of the PP/DEHP composite trix, the crystalline portion of the composites was evaluated from the
two absorption peaks at 998 and 973 cm−1, which were known as the
Although the mechanism through which plasticizers act is simple, it crystalline and the amorphous segments of PP [15]. The crystalline com-
has not yet been fully understood. Several existing proposed mecha- ponent was estimated through the differences in intensity between
nisms stipulate that plasticizers act as an internal lubricant by deterio- A998/A973, and is presented in Table 1. As shown in Table 1, the high
rating the intermolecular interactions that exist between the molecular weight iPP250 had a higher crystalline nature than the low
polymeric chains, and may increase the free volume. Hence, polymer molecular weight iPP12 and aPP/DEHP composites. The crystallinity
flexibility is enhanced when the plasticizers intercalate between the ratio of iPP12 and aPP14 exhibited significant variation. However,
polymers chains, and increase the distance between the molecules iPP12 and aPP14 were similar upon being mixed with DEHP due to
without affecting the microcrystalline portions of the polymer, thus the plasticizer packing on the amorphous portion, rather than the crys-
promoting the mobility of the polymer chains, and leading to a reduced talline portion, due to its chain flexibility.
glass transition temperature [11]. PP-based blood-component packing
materials were fabricated with DEHP as a plasticizer, and the relation-
ship between DEHP and PP was studied. With the incorporation of 3.2. Morphology of the PP/DEHP composites
DEHP as an additive, the physical properties of PP such as melting tem-
perature, crystallization, and morphology were greatly influenced in the The morphologies of the PP/DEHP composites were compared after
composite. Hence, it is essential to investigate the issues regarding the the DEHP migration analysis, and are presented in Fig. 3. From this

Fig. 3. Morphological observations of iPP/DEHP composites from iPP250, iPP12 and amorphous aPP. (a, d and g are as prepared: b, e and h are after performed at 25 °C release: c, f and i are
after performed at 90 °C).
 A. Prasannan et al. / Reactive and Functional Polymers 113 (2017) 70–76
figure, it can be observed that the aPP14/DEHP composite had a gum--
like morphology, while the iPP250/DEHP and iPP12/DEHP composites
had a sheet-like morphology. After the migration analysis carried out
25 °C, the morphology of the corresponding samples did not change
(Fig. 3b, e, and h). As the temperature of the DEHP analysis was in-
creased to 90 °C, the surface morphology of the samples became rough-
er (Fig. 3c, f, and i) in comparison to that of the samples treated at the
lower temperature. The morphology of the iPP12/DEHP composites
was not affected by the DEHP migration analysis at 25 °C and 90 °C,
thus revealing the existence of fewer interactions between the plasticiz-
er and iPP12. The aPP14/DEHP composites appeared to have a bulky ag-
glomerated surface. However, they gained a relatively smooth surface
after the DEHP migration was carried out at 25 °C, and as the tempera-
ture for the DEHP migration was increased to 90 °C, aggregated particles
with a smooth surface appeared.
3.3. Thermal stability of the PP blend
The thermal stability of the PP/DEHP composites was evaluated by
means of a TGA analysis before and after the DEHP migration analysis,
as shown in Fig. 4. The thermal degradation temperature (Td) of neat
iPP250 started at about 410 °C, with a single-step degradation, and it de-
creased to about 200 °C (with a two-step degradation) after DEHP was
added. This two-step degradation is attributed to the degradation of
DEHP and the polymer backbone. The high molecular weight iPP250
had the highest thermal stability due to its molecular stereo-arrange-
ment in the crystal packing. A reduction of Td was also observed for
the low molecular weight iPP12 and amorphous aPP14, going from
330 °C to 202 °C and 371 °C to 208 °C, respectively. The thermal stability
of iPP250 and its composites exhibited a different Td than its counter-
parts. From the results, iPP250/DEHP started degrading at around
210 °C. Upon the sample being soaked in water at 25 °C for the DEHP mi-
gration studies, the Td was observed at 214 °C. When the DEHP migra-
tion studies were carried out at 90 °C, significant thermal stability was
obtained, with the Td increasing to 229 °C. Such thermal stability of
the high molecular weight iPP250 is due to its molecular stereo-ar-
rangement in the crystal packing, which is more dominant in high mo-
lecular weight iPP than low molecular weight iPP. The stereo crystal
packing arrangement of iPP250 was disturbed when DEHP was intro-
duced into the polymer matrix because of its plasticizer nature, and
therefore the crystal arrangement became randomly organized. In addi-
tion, upon the DEHP removal process, the incorporated DEHP moieties
started to migrate from the polymer, and subsequently induced poly-
mer recrystallization. Such a reformation of the polymer crystals during
the DEHP migration can cause denser crystal packing. In the case of the
low molecular weight iPP12 and amorphous aPP14, such DEHP-migra-
tion-induced crystal packing does not occur because their lower crystal-
line and amorphous nature is more dominant. Hence, the thermal
stability of iPP250 can be enhanced while the plasticizers migrate, and
the intermolecular distances between the molecules can be decreased
Fig. 4. The thermal stability of the iPP blends with DEHP, (a) isotactic Mw ~ 250,000, (b) isotactic Mw ~ 12,000 and (c) amorphous, Mw ~ 14,000.
73
through the formation of polymer microcrystalline portions, which
can promote the stability of the polymers chains.
3.4. Crystallinity evaluation
The addition of a plasticizer into a polymeric matrix can induce the
weakening of intermolecular interactions, and influence the melt be-
havior of the polymer by enhancing the polymer free-volume and mo-
bility of the chains. Hence, an assessment of the melting properties of
the polymer matrix is sensible and essential to understand the packing
of DEHP while it is migrating. Fig. 5(a) and (b) show the melting behav-
ior of various PP/DEHP composites, along with the DEHP migration per-
formance. The PP/DEHP composites exhibited a lower melting
temperature than pristine PP, and similar behaviors were observed
after the DEHP migration experiments conducted at 25 °C and 90 °C.
The reduction of the melting temperature is due to the incorporated
DEHP in the PP crystals, which can enhance the mobility of the polymer
chains and increase the free-volume of PP. Significant melting tempera-
ture changes were observed in the low molecular weight iPP12, rather
than in the high molecular iPP250, because of its dominant amorphous
portions. A single fusion endotherm dominated the low molecular
weight iPP12, and after the incorporation of DEHP, this endotherm
was shifted to a lower temperature from the obvious peak position. In
addition, a shoulder appeared before the melting peak after the incorpo-
ration of DEHP, which reveals that the PP/DEHP composites have less
symmetry and two different crystal domains. In order to understand
the crystallization behavior of PP in the presence of DEHP, the crystalli-
zation temperature was monitored, as shown in Fig. 5(c) and (d). In
polymers, the addition of a plasticizer may increase the mobility of the
polymers chains and reduce the crystallization temperature. A reduc-
tion of the crystallization temperature was observed in all PP/DEHP
composites. The low molecular weight iPP12/DEHP composite exhibit-
ed a small shoulder due to the two different crystallizations, or the reor-
ganization of the crystals that occurred during the crystallization, and is
consistent with the melting behavior. The shoulder at the low tempera-
ture peaks may be attributed to the different crystal domains of PP. This
is due to the distribution of DEHP in the semi-crystalline domains of iPP,
with dominated portion of amorphous regions that can interact with
the functional groups of DEHP. However, the crystallization peak of
high molecular weight iPP250/DEHP did not have an influence during
the DEHP migration due to the reformation of a perfect semi-crystalline
structure (Table 1). As shown in Table 1, the degree of crystalline por-
tions depends on the molecular weight. This indicates that for iPP/
DEHP, the crystalline regions decreased linearly upon decreasing the
molecular weight. This is believed to result from the molecular arrange-
ment of the oriented long polymer chains to efficiently pack into a crys-
tal lattice. At high molecular weights, different parts of the same chain
probably crystallize into separate folded-chain lamellae, which are re-
sponsible for the higher crystalline portions. Although lower molecular
weight polymer chains may have orientation, they form less perfectly
74 A. Prasannan et al. / Reactive and Functional Polymers 113 (2017) 70–76

Fig. 5. DSC fusion endotherms for iPP blends with DEHP (a) melting of iPP12; (b) melting iPP250; (c) crystallization of iPP12; and (d) crystallization of iPP250.

folded chain crystals due to the greater concentration of end group de-
fects [16], and the absence of same chain crystallization in the lamellae,
leading to a lower degree of crystalline regions. Therefore, crystal de-
fects from polymer chain ends and folded-chain crystals, which are
the main contributors to the degree of crystallization, vary with molec-
ular weight. In addition, a drastic alteration may occur in the inter and
intramolecular structure of the polymer chains associated with lattice
crystalline packing upon the addition of DEHP, which is a factor that is
also connected with the molecular weight of the polymers.
WAXD pattern analysis was used to understand the influence of
DEHP on the low and high-molecular weight PP in composites. Fig. 6
shows the WAXD patterns of neat PP and PP/DEHP composites, and
the orientation of the crystallographic planes after the DEHP migration
analysis was carried out at different temperatures. The high-molecular
weight iPP250 exhibited five distinct crystalline peaks of the α-form
of iPP [17]. Significant intensity changes were observed in the main
(110) and (040) orientation planes upon DEHP migration. In the case
of low molecular weight iPP12, reorientation was observed with a con-
tinuous increase of the (040) plane, and a systematic increase of the
(110) plane was also observed for the low molecular weight iPP12/
DEHP composites. Similarly, other orientation planes such as (130),
(111), and (131) showed an increased reorientation with DEHP

Fig. 6. WAXD pattern of (a) iPP12 and (b) iPP250 and after DEHP migration analysis.
 A. Prasannan et al. / Reactive and Functional Polymers 113 (2017) 70–76
Fig. 7. DEHP migration assay though the UV–Visible spectroscopy.
addition. This could be a response to the amount of amorphous phase
that may hold the DEHP in the PP matrix. In the iPP12/DEHP composite,
it is possible that the DEHP plasticizers acted on the amorphous phase;
hence iPP12 with a large number of amorphous domains could appre-
ciably accommodate more DEHP. Once DEHP migrated from the amor-
phous portion of the polymer matrix, reorientation with crystal
growth occurred in iPP12/DEHP. The WAXD pattern results confirmed
the reorientation of the PP crystalline matrix during the addition of
DEHP. This reorientation was sustained even after the DEHP had migrat-
ed. This was not the case for high molecular weight iPP. Based on the
DSC and WAXD pattern results, DEHP accommodations in the iPP poly-
meric matrix may be compatible with the amorphous phase rather than
the crystalline phase of PP.
3.5. DEHP migration
The DEHP migration studies were performed using a UV–visible
spectrometer with a full scan analysis, and at 272 nm [18]. As shown
in Fig. 7, significantly high absorption peaks appeared for iPP12, espe-
cially when the analysis was performed at 90 °C. The adsorption value
of amorphous aPP14/DEHP at 90 °C (0.0186) was slightly lower than
the one at 25 °C (0.0273). For the high molecular weight iPP250/
DEHP, the absorption value at 272 nm was almost the same (0.006 ±
0.0002) in the high and low temperature migration analyses, thus
revealing that there was fewer DEHP released at high and low
temperatures, and that the migration behavior was not dependent on
Fig. 8. DEHP migrations assay though the UV–Visible spectroscopy by Liquid chromatography-mass spectrometry and corresponding calibration curve.
75
temperature. This is due to the perfect crystalline packing of the high
molecular weight iPP250/DEHP. Moreover, the DEHP migration was
lower in the high molecular weight iPP250 due to its high molecular
weight. This is due to the DEHP moiety being able to entangle between
the polymer chains, making it harder to migrate from the polymer crys-
tals. In addition, liquid chromatography-mass spectrometry (LC/MS)
was used to evaluate the DEHP migration though the use of a calibration
curve.
The results from LC/MS are shown in Fig. 8. The DEHP migration was
highest for the low molecular weight iPP12 at 90 °C and 25 °C. For amor-
phous aPP14/DEHP, the migration of DEHP was similar to that of iPP12,
and the temperature did not influence the migration of the plasticizer
because of the dominant amorphous regions. The lowest migration
was observed for the high molecular weight sample of iPP250. For this
sample, the migration of DEHP at 25 °C was smaller than at the higher
temperature, which is consistent with UV–Vis results. During the migra-
tion of DEHP, the molecular weight and crystalline portion of PP can in-
fluence the packing of DEHP, as DEHP prefers to pack in the amorphous
rather than crystalline regions. Both the DSC and WAXD results revealed
that low molecular weight iPP12 exhibited fewer crystalline regions.
Perhaps the migration of DEHP mainly depends on the amorphous re-
gions of the polymer, where DEHP packed efficiently.
Among the three different molecular weight PP/DEHP composites,
high molecular weight iPP250 released a significantly lower amount of
DEHP even at the higher temperature. While the low molecular weight
iPP12/DEHP showed a release behavior about 26% faster at high temper-
atures than at lower temperatures. Comparing the results obtained at
both temperatures, both the high and low molecular weight iPP/DEHP
composites released more DEHP at 90 °C. However, the difference in
the plasticizer release percentage between the high and low-tempera-
ture treatments was about 1% for the amorphous aPP14/DEHP compos-
ites, revealing that the molecular weight of PP influences the packing
and release of the plasticizer.
Fig. 9 shows the possible release mechanism of the plasticizer. The
release of the plasticizer mainly depends on the molecular weight of
the polymer matrix, as the plasticizer may stabilize in both the crystal-
line and amorphous regions of PP, with the amorphous region having
a bigger contribution on the plasticizer's controlled-release rate. In the
case of low molecular weight iPP12, the plasticizer could easily adopt
in the amorphous region of PP due to their molecular packing through
the chain flexibility, and therefore higher migration levels were record-
ed. High molecular weight iPP250 was constructed through three-di-
mensional packing because of its high crystalline nature. Moreover,
high-molecular-weight-based composites may contain many small
crystals domains, and therefore can strongly hold the plasticizer and
slow down its release. Hence, the above results reveal that high molec-
ular weight iPP250 is more suitable for the fabrication of blood-compo-
nent packing materials with a lower migration of DEHP.
76 A. Prasannan et al. / Reactive and Functional Polymers 113 (2017) 70–76
Fig. 9. Schematic illustration of DEHP releasing with influence of molecular weight of polymer matrix.
4. Conclusions
In summary, a novel composite material made of polypropylene and
DEHP was prepared to evaluate the migration of DEHP. For this purpose,
three different molecular weights of polypropylene were used, and their
DEHP-releasing ability was evaluated at two different temperatures.
The release behavior of DEHP was affected by the molecular weight of
PP, and the crystalline nature of iPP. Among the three different molecu-
lar weight PP/DEHP composites, the high molecular weight iPP250 re-
leased a significantly lower amount of DEHP due to their crystalline
nature with three-dimensional packing, which can strongly hold onto
the plasticizer. The present study showed that high molecular weight
iPP/DEHP composites may be suitable for blood-component bag mate-
rials due to their low DEHP migration.
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