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Synthesis and Properties of Hydrogels From Poly (Vinyl Alcohol) and Ethylenediaminetetraacetic Dianhydride
Synthesis and Properties of Hydrogels From Poly (Vinyl Alcohol) and Ethylenediaminetetraacetic Dianhydride
www.elsevier.nl/locate/polymer
Abstract
Crosslinked poly(vinyl alcohol) with different amounts of ethylenediaminetetraacetic dianhydride was synthesized and characterized by
c ; the mesh size (j ) and the
elemental analysis, 13C-NMR and IR spectroscopy. The average molecular weight between crosslinks M
crosslinking density (r x) were calculated from swelling studies and related to OH/anhydride ratios. The polymer-solvent interaction
parameter (x ) was calculated by mechanical measurements. The swelling behaviour of hydrogels was studied as a function of the crosslinking degree. A kinetic study of the absorption determined the transport mechanism. The diffusion coefcient was calculated for the Fickian
mechanism, and the swelling behaviours were analyzed in buffer solutions at various pH and temperature ranges. Swelling ratios were
relatively high and sensitive to pH and ionic strength, but not to temperature. q 2001 Published by Elsevier Science Ltd.
Keywords: Hydrogels; Poly(vinyl alcohol); Ethylenediaminetetraacetic dianhydride
1. Introduction
Poly(vinyl alcohol) (PVA) hydrogels are widely used in
cooling media, contact lenses and material for drug delivery
systems [1]. The hydrophilicity of such hydrogels can be
enhanced by incorporating ionizable functional groups such
as the carboxylic groups. Polyelectrolytes are polymers that
contain relatively ionizable groups at levels ranging from a
few mol% to 100% of the repeating units.
Much attention has been directed in recent years to polyelectrolyte-type hydrogels that undergo controllable volume
changes in response to small variations in solution conditions [2]. Temperature and pH are the normal solution
variables in physiological, biological and chemical systems
[1,3]. Temperature- and pH-sensitive gels have been
suggested for a variety of novel applications, including
controlled drug delivery [4,5].
In this study we prepared hydrogels of PVA crosslinked
with ethylenediaminetetraacetic dianhydride (EDTAD) and
as a result of crosslinking, ionizable carboxylic acid groups
were introduced to the network. In a previous study we
investigated the crosslinking of PVA with several
carboxylic acid dianhydrides [6], a type of crosslinker that
is not frequently used with PVA, to obtain tridimensional
polymers. These polymers had a high degree of crosslinking
* Corresponding author.
E-mail address: cadiz@quimica.urv.es (V. Cadiz).
0032-3861/01/$ - see front matter q 2001 Published by Elsevier Science Ltd.
PII: S 0032-386 1(01)00082-9
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Scheme 1.
OH/anhydride
(molar ratio)
Theoretical
(wt% N)
EA
(wt% N)
DSC Tg
(8C)
PVAEDTA 25
PVAEDTA 10
PVAEDTA 5
PVAEDTA 3.3
PVAEDTA 2.5
PVA
1/0.250
1/0.100
1/0.050
1/0.033
1/0.025
4.0
2.1
1.1
0.8
0.6
3.5
2.0
1.1
0.7
0.6
53
46
43
41
40
41
n
ln1 2 n2m 1 n2m 1 xn22m
1
2
V1 "
#
c M
n 2
M
n2m 1=3 2 n2m
n2r
2
n2r
f n2r
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Fig. 1. 13C-NMR spectra of PVA and hydrogel PVAEDTA 25 (OH/anhydride 1/0.250) recorded in D2O with ACN as reference.
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Table 2
c ; effective
Swelling and mechanical characterization results: PVAEDTAwater interaction parameter (x ), average molecular weight between crosslinks M
crosslinking degree (n e/V0) and Young modulus (E)
Sample
OH/anhydride
(molar ratio)
c (g/mol)
M
(swelling eq.)
c (g/mol)
M
(mechanical eq.)
n e/V0 10 3
(mol/l)
E
(KPa)
PVAEDTA 25
PVAEDTA 10
PVAEDTA 5
PVAEDTA 3.3
PVAEDTA 2.5
1/0.250
1/0.100
1/0.050
1/0.033
1/0.025
0.527
0.519
0.504
2720 a
5380 a
7180 a
7300 b
7490 b
3400
5700
7260
202
55
5.5
199
33
3
a
b
c calculated
the comparison of the experimental values of M
from elastic modulus or swelling data is more accurate
(Table 2).
r2
c
M
2
ne
2r
1 2
V0
Mn
Here, r 2 is the density of dry hydrogel and (n e/V0) is the
effective crosslinking degree.
This effective network chain concentration (n e/V0) can be
calculated from the stress compression-strain modulus for
small deformations using the following equation [16]:
ne
2=3
22
ts
3
RT n1=3
2m n2r a 2 a
V0
Here, t s is the applied force per unit area of swollen hydrogel, R is the gas constant, T is absolute temperature, and a is
the deformation ratio a L=L0 $ 0:95: Fig. 3 shows the
plot of the stress of the swollen hydrogel against the strain
expressed as a 2 1100: From the slopes we can calculate
elastic moduli (E) and from a plot of t s against a 2 a22 ;
which is linear at low deformations, we can also calculate
(n e/V0). All these values are given in Table 2, where, as
rx
1
n M c
Table 3
Swelling characterization results: average molecular weight between cross c ; mesh size (j ) and crosslinking density (r x)
links M
Sample
OH/anhydride
(molar ratio)
c
M
(g/mol)
Mesh size
)
j (A
r x 10 4
(mol/cm 3)
PVAEDTA 25
PVAEDTA 10
PVAEDTA 5
PVAEDTA 3.3
PVAEDTA 2.5
1/0.250
1/0.100
1/0.050
1/0.033
1/0.025
2720
5380
7180
7300
7490
88
143
227
286
517
4.82
2.53
1.78
1.72
1.69
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