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Article history:
Received 27 October 2011
Received in revised form 4 January 2012
Accepted 5 February 2012
Available online 24 February 2012
Keywords:
PVC plastisol
Plasticizer
Cyclodextrin derivative
Migration inhibitor
Gelation and fusion process
a b s t r a c t
We successfully evaluated the effects of 2,3,6-per-O-benzoyl-b-cyclodextrin (Bz-b-CD) on
the rheological properties of PVC plastisols and the migration behavior of plasticizer from
exible PVC. Two types of plasticizer, di-isononyl phthalate (DINP) and diisononyl cyclohex-4-ene-1,2-dicarboxylate (Neocizer), along with Bz-b-CD as a migration inhibitor were
mechanically mixed into an emulsion grade PVC resin to prepare plastisols. The presence of
Bz-b-CD was expected to facilitate formation of stable complexes with DINP or Neocizer in
the exible PVC. It was necessary to determine whether changes in the processing conditions of the PVC plastisol were needed for use in this application. To this end, the viscoelastic properties of the plastisols, including the elastic modulus, G0 , and the viscous modulus,
G00 , were continuously monitored as a function of temperature during the gelation and
fusion processes using rheological analysis techniques. The results showed that complete
gelation was slightly delayed and both moduli (G0 and G00 ) decreased upon addition of
Bz-b-CD to the PVC matrix. FE-SEM images yielded insight into the gelation and fusion
processes. The curing conditions and physical properties of the exible PVCs containing
Bz-b-CD were optimized, and the inuence of Bz-b-CD on the migration of the plasticizers
and the stability of the exible PVC was studied. The results showed that Bz-b-CD reduced
migration of DINP and Neocizer from the exible PVC by almost 40% and 25%, respectively,
thereby favorably restricting migration within the exible PVC.
Crown Copyright 2012 Published by Elsevier Ltd. All rights reserved.
1. Introduction
Plasticizers are additives that can improve the exibility
and workability of poly(vinyl chloride) (PVC) by forming
secondary bonds (dipoledipole interactions) with the
polymer chains. The high density of the ends of the plasticizer chains introduces additional free volume into the PVC
matrix [1]. PVC can be plasticized with varying amounts of
plasticizers to form exible PVC. Phthalate plasticizers,
such as di-isononyl phthalate (DINP) and di-(2-ethylhexyl)
phthalate (DEHP), are common plasticizers that are widely
used in industrial applications [2]. Phthalate plasticizers
weakly interact with PVC chains and may migrate out of
Corresponding author. Tel.: +82 2 880 8365; fax: +82 2 885 1748.
E-mail address: sykwak@snu.ac.kr (S.-Y. Kwak).
0014-3057/$ - see front matter Crown Copyright 2012 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2012.02.008
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a r t i c l e
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Table 1
Compositions of the PVC plastisols.
Sample codes
PVC/DINP
PVC/DINP-CD
PVC/Neo
PVC/Neo-CD
a
b
c
Components (phr)a
PVC resin
DINP or Neocizer
ESOb
TSc
Bz-b-CD
100
70
10
10
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Fig. 2. FT-IR spectra of (a) b-CD, (b) benzoyl chloride, and (c) Bz-b-CD.
range 10291157 cm1 were assigned to primary and secondary COH stretches, and to the COC antisymmetric
stretches, respectively [17]. Modication of the neat b-CD
with benzoyl chloride, however, introduced signicant
changes to the FT-IR spectrum of Bz-b-CD, as can be seen
in Fig. 2(c). The broad peak corresponding to the hydroxyl
group stretch disappeared and was accompanied by the
appearance of peaks corresponding to the sp2 CH stretch
at 3075 cm1 and the aromatic C@C at 1603 and
1448 cm1. These bands corresponded to stretches of the
aromatic ring of the benzoyl group. In addition, the conjugated C@O stretches at 1729 cm1 and the CO stretches in
the range 10001300 cm1 resulted from formation of an
ester. Therefore, the Bz-b-CD spectrum clearly indicated
that b-CD had been modied. Fig. 3 shows the 1H NMR
spectra of neat b-CD, benzoyl chloride, and Bz-b-CD. 1H
NMR spectroscopy provided additional evidence for the
modication and indicated the degree of substitution.
The Bz-b -CD spectrum showed that the hydroxyl group
peaks of b-CD disappeared as the peaks attributed to the
protons of the benzoyl group appeared (2,3,6-COC6H5 at
6.98.1 ppm), indicating the substitution of the three hydroxyl groups of b-CD. Each proton (3-H triplet at
6.2 ppm, 1-H doublet at 5.6 ppm, 2-H doublet of doublets
at 5.1 ppm, 5-, 6a-, 6b-H, at 4.85.0 ppm, and 4-H triplet
at 4.5 ppm, respectively) of the Bz-b-CD was detected,
and the peaks were shifted downeld upon modication
(see Fig. 3(c)). The number of benzoyl groups, x, introduced
to neat b-CD (which included 21 hydroxyl groups) was easily calculated from the relative peak integrals in the 1H
NMR spectrum. The value of x was determined to be 20.2
(around 96%), which conrmed the successful modication
of neat b-CD to yield Bz-b-CD. Additional discussion of the
modication and general characterization of Bz-b-CD is
provided in our previous publication [9].
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Fig. 3. 1H NMR spectra of (a) b-CD, (b) benzoyl chloride, and (c) Bz-b-CD.
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Fig. 4. Particle size distributions of Bz-b-CD (solid black bar) and neat
b-CD (shaded gray bar) in (a) DINP and (b) Neocizer.
became essentially complete is indicated by the intersection of the moduli (G0 and G00 ). The processability requirements for PVC plastisol processing emphasize the
viscoelastic behavior, such gelation and fusion, of the
plastisol [24]. During gelation and fusion, the elastic and
viscous modulus in the rheological measurements underwent important changes. Fig. 5 shows the changes in G0
and G00 for the PVC/DINP and PVC/DINP-CD plastisols,
respectively, which were recorded as a function of temperature. The viscoelastic behavior obtained from PVC/DINPCD was similar to that of PVC/DINP. The maximum of the
modulus corresponded to the complete gelation and onset
of fusion. In this stage, the PVC particles became swollen as
the plasticizer was taken up, and some portion of the PVC
molecules may have dissolved into the plasticizer from the
surface layers of the particles. Further temperature increases resulted in a decrease in the modulus, indicating
the dominance of fusion and melting of the PVC microcrystallites. The decreased modulus was due to two processes:
(i) the normal temperature-dependent changes were primarily attributable to thermal expansion, and (ii) melting
of the PVC microcrystallites [25]. As can be seen Fig. 5,
complete gelation of the PVC/DINP-CD plastisols occurred
at 158 C, a gelation temperature that was slightly higher
than that of the PVC/DINP plastisol (150 C). Gelation of
the PVC plastisols was delayed upon addition of Bz-b-CD
particles, possibly because of the decreased interaction of
the PVC with the plasticizer. In the Neocizer series, the
gelation point of the PVC/Neo-CD plastisol was 169 C,
slightly higher than the gelation point of the PVC/Neo plastisol (162 C). Gelation of the PVC plastisol was also
delayed by the addition of Bz-b-CD particles, as shown in
Fig. 6. The formation of entanglements among the PVC
chains may have been blocked by the Bz-b-CD nanoparticles (see Fig. 7(b)). During processing, partial melting of
the crystallites in the primary PVC particles occurred,
allowing the macromolecules to diffuse through the
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boundaries and entangle among the other macromolecules, as shown in Fig. 7(a). The melted crystalline components then recrystallized during cooling to form newly
created ordered domains of secondary crystallites [26].
The presence of well-dispersed Bz-b-CD nanoparticles in
the PVC matrix may have disrupted the physical crosslinks
between neighboring PVC molecules, thereby partially
interrupting formation of the 3-D macromolecular
Fig. 7. Formation of molecular entanglement; (a) neat PVC and (b) PVC with Bz-b-CD.
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Fig. 8. DSC curves for non-plasticized PVC and exible PVC samples.
with those of pure exible PVCs. The addition of plasticizers to a PVC resin increased the free volume of the PVC,
thereby lowering the PVC Tg. The exibility of PVC is a
main reason why these materials are used so widely. The
percent plasticization efciency, EDTg, can be calculated
according to the following equation:
EDT g
DT g;PVC=plasticizerCD
100
DT g;PVC=plasticizer
EDeb
Deb;PVC=plasticizerCD
100
Deb;PVC=plasticizer
The eb values of the exible PVC samples and the calculated EDeb values are also presented in Table 2, and the
trends differ only slightly from those observed for the EDTg
data. The transmittance and haze of the exible PVC sheets
containing Bz-b-CD were investigated and compared with
their counterparts, PVC/DINP and PVC/Neo. In general,
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c
d
PVC
PVC/DINP
PVC/DINP-CD
PVC/Neo
PVC/Neo-CD
Tg (oC)a
EDTg (%)b
eb (%)c
EDeb (%)d
85.6
0
163.2
0
47.3
100.0
767.6
100.0
44.4
97.8
710.1
90.5
40.9
100.0
657.3
100.0
38.8
98.3
622.7
92.9
Fig. 10. Transmittance (striped bar) and haze (shaded bar) of the exible
PVC sheets.
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a
b
Data
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C PVC=plasticizerCD
100
Anti-migration efficiency% 1
C PVC=plasticizer
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Table 3
Concentration of the plasticizer and anti-migration efciencies as a
function of time.
Samples
PVC/DINP
PVC/DINP-CD
Anti-migration efciencies (%)
PVC/Neo
PVC/Neo-CD
Anti-migration efciencies (%)
1 day
3 day
5 day
7 day
4.89
2.89
40.86
7.03
5.27
24.98
6.26
3.66
41.64
8.84
6.56
25.83
6.66
4.10
38.46
9.75
7.13
26.88
6.86
4.25
38.11
10.11
7.70
23.86
where CPVC/plasticizer-CD and CPVC/plasticizer are the concentration of the migrated plasticizer during migration in the
PVC/plasticizer-CD and PVC/plasticizer samples, respectively. The anti-migration efciencies of PVC/DINP-CD
and PVC/Neo-CD were 38.11% and 23.86%, respectively.
This indicated that the presence of Bz-b-CD in the exible
PVC matrix dramatically reduced plasticizer migration,
which was attributed to the formation of an inclusion complex between the Bz-b-CD cavity and the plasticizer, and
stabilizing pp associations between the benzoyl groups
of Bz-b-CD and the aromatic ring of the plasticizer molecules. Bz-b-CD, which hindered migration of the plasticizer, also will block the plasticizer molecules by winding
pathway (also called tortuous pathway) effect. In other
words, it would promote the path length for transporting
plasticizers and results in a decrease of plasticizer migration (see Fig. 12). Neocizer did not introduce pp contacts,
and only van der Waals interaction stabilized the interactions between Bz-b-CD and Neocizer. For this reason, the
reduction in the rate of Neocizer migration (with an aliphatic ring) was smaller than the reduction in the rate of
DINP migration (with an aromatic ring). Differences in
the structure strongly affected the plasticizer/Bz-b-CD
interaction process. In addition, gel permeation chromatography (GPC) results conrmed that Bz-b-CD was not released from the exible PVC sheets during the migration
Fig. 12. Schematic illustration of the anti-migration mechanism of the plasticizer in the PVC matrix.
[9]
[10]
4. Conclusion
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[15]
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[19]
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