J Polym Res (2015) 22:233
DOI 10.1007/s10965-015-0876-2
ORIGINAL PAPER
New superabsorbent hydrogels synthesized by copolymerization
of acrylamide and N-2-hydroxyethyl acrylamide with itaconic
acid or itaconates containing ethylene oxide units in the side chain
Amal El Halah 1 & Jesús Contreras 1 & Luis Rojas-Rojas 1 & Mariel Rivas 1 &
Milagros Romero 1 & Francisco López-Carrasquero 1
Received: 29 June 2015 / Accepted: 4 November 2015
# Springer Science+Business Media Dordrecht 2015
Abstract A series of acrylamide/itaconic acid (AAm/IA),
acrylamide/monomethoxyethyl itaconate (AAm/MEI), and
acrylamide/dimethoxyethyl itaconate (AAm/DEI) hydrogels
were synthesized in AAm/comonomer molar ratios of 100/0,
90/10, 80/20, and 70/30. In all cases, almost quantitative
yields were obtained, and the swelling ability increased when
comonomer proportion increased. AAm/MEI and AAm/IA
reach swelling values more than 40,000, and both systems
swelled more than AAm/DEI. This fact pointed out that the
carboxylic acid groups present in IA and MEI are mainly
responsible for the swelling. All of these hydrogels are stable
up to 150 °C as indicated by the TGA measurements. For
comparison, the synthesis of a series of N-2-hydroxyethyl
acrylamide/itaconic acid (HEAAm/IA), N-2-hydroxyethyl ac-
rylamide /monomethoxyethyl itaconate (HEAAm/MEI), and
N-2-hydroxyethyl acrylamide /dimethoxyethyl itaconate
(HEAAm/DEI) hydrogels were also carried out. The swelling
behavior of HEAAm/IA and HEAAm/MEI was opposite to
the former; in these cases the presence of the itaconate como-
nomer diminish the swelling ability. A diffusion mechanism
study was carried out for all the series.
Keywords Superabsorbents hydrogels . Acrylamide .
N-2-hydroxyethyl acrylamide . Itaconic acid .
Monomethoxyethyl itaconate . Dimethoxyethyl itaconate
* Jesús Contreras
jeco@ula.ve
1
Grupo de Polímeros, Departamento de Química, Facultad de
Ciencias, Universidad de Los Andes, Mérida 5101-A, Venezuela
Introduction
The gels are polymeric networks three-dimensional crosslinked
and swollen with fluid. The term hydrogel is used to refer to
those gels that are specifically characterized by their extraordi-
nary ability to absorb water or aqueous solutions (e.g., body
fluids) and retaining its network structure after swelling [1]. The
polymeric hydrogels are characterized by softness, elasticity,
insolubility in water, swelling with water, and hydrophilicity
[2]. The hydrophilicity of these materials is due to the presence
of water compatible groups such as –OH, –COOH, –CONH2,
or –SO3H, and those are related to the existence of capillary
areas and differences in osmotic pressure [3]. The features of
the constituent monomers and the crosslinking degree deter-
mine the swelling properties of the dry hydrogel (xerogel)
and, therefore, its field of application. Thus, hydrogels play
important roles in many fields; for example, they are used in
superabsorbent materials [2–6], drug-delivery carriers [7, 8],
waste water decontamination processes [9–11], catalyst carriers
[12, 13], smart materials [14], and tissue engineering [15, 16].
These materials are obtained by polymerization and simul-
taneous crosslinking of one or more polyfunctional monomers
to form a three dimensional network [17]. The most efficient
water absorbents are polymer networks that carry dissociated
ionic functional groups [18]. Itaconic acid (IA) is a natural
source water soluble monomer having two carboxylic acid
groups that are able to be esterified selectively [19]. IA and
its esters can easily copolymerize with acrylamide (AAm) and
provide polymer chains with carboxylic side groups, which
are highly hydrophilic and are able to form hydrogen bonds
[20, 21]. At this point, it is worth mentioning that AAm/IA
hydrogels with very low IA amounts have been prepared pre-
viously [22–26]. These small amounts of IA comonomer in
the gel network generally introduce pH sensitivity and in-
crease the degree of swelling [23–25]. For these reasons IA
233 Page 2 of 10
and its derivatives offer interesting possibilities to be used as
comonomers in the synthesis of superabsorbent hydrogels or
as functional polymers. Preparation of poly(N-2-hydroxyethyl
acrylamide) and hydrogels based o N-2-hydroxyethyl acryl-
amide (HEAAm) was also studied [27, 28].
In this work, we reported on the synthesis, characterization,
degradation, and swelling studies of AAm/IA, AAm/MEI,
and AAm/DEI hydrogels prepared in various molar ratios.
The effects of monomer ratio, the nature of the itaconate de-
rivative, the solvent used for synthesis and time on the swell-
ing in water were investigated and the results compared with
those obtained when AAm were substituted by HEAAm. The
diffusion process of water molecules was also studied.
Experimental
Materials
Itaconic acid (IA) (Aldrich), methoxyethanol (Aldrich), acryl-
amide (AAm) (Aldrich), N-2-hydroxyethyl acrylamide
(HEAAm) (Aldrich), ammonium persulfate (APS) (Riedel-
de Haën), and N, N′-methylenebis(acrylamide) (MBAm) (Ul-
trapure Bioreagent GT) were used without further purifica-
tion. Double distilled water was used for the polymerization
reactions and swelling studies. Other solvents were used as
received. Monomethoxyethyl itaconate (MEI) and
dimethoxyethyl itaconate (DEI) were prepared by the method
previously described [21, 29].
Synthesis of hydrogels
Synthesis of hydrogels was carried out in water or in a water/
ethanol 60/40 (V/V) mixture, using APS as initiator and
MBAM as crosslinking agent both 1 % respect to the total
moles of comonomers. The synthesis was performed accord-
ing the following procedure: Predetermined amounts of co-
monomers (AAm or HEAAm together IA, MEI, or DEI) were
dissolved in the chosen solvent (water or water/ethanol 60/40
V/V) in a glass tube (A). In another tube (B), amounts required
of the initiator and crosslinking agent were dissolved in 2 mL
of the same solvent used to prepare solution A. This solution
was added into the tube A. Then the reaction mixture was
purged with nitrogen gas for 5 min to eliminate dissolved
oxygen, and the reaction tubes were placed in a thermostatic
bath at 60 °C for 24 or 48 h. At the end of the polymerization,
the hydrogels were taken out by breaking the glass tubes.
Fresh hydrogels obtained in long cylindrical shapes were cut
into fine pellets, and were washed several times with the sol-
vent used in the synthesis. Finally, the hydrogels were air-
dried at room temperature for several days until constant
weight. The hydrogel chemical structure was confirmed by
FTIR spectroscopy.
J Polym Res (2015) 22:233
Characterization
Infrared spectra of the hydrogels were recorded on a Perkin-
Elmer 2000 instrument from KBr pellets with xerogel sam-
ples. All the spectra were obtained with 32 scans and spectral
resolution of ±4.
Thermogravimetric analyses, TGA, were carried out on a
Perkin-Elmer TGA-7 thermobalance. Samples of about 5 mg
were heated at a rate of 10 °C/min under an ultra-pure nitrogen
atmosphere for temperatures ranging from 25 to 500 °C.
Thermal volatilization analyses, TVA, were performed in a
vacuum line, heating samples of about 100 mg from room
temperature to 350 °C during 30 min under a moderate pri-
mary vacuum. Gases or non-condensing fractions were col-
lected in a gas cell equipped with KBr windows at liquid
nitrogen temperature and volatile fractions condensing at
room temperature were collected in the so-called cold ring.
The different fractions were then analyzed by FTIR
spectroscopy.
The morphology of xerogels was evaluated through SEM
images from the surface of lyophilized swollen samples. For
this purpose, the samples were swollen to equilibrium, cooled
in liquid nitrogen, and then lyophilized in a LABCONCO
apparatus during 24 h. The images were obtained using a
scanning electron microscope (HITACHI S-2500) operating
at 12 kV with a magnification of 500 times. Before the analysis,
the aerogel samples were coated with a thin layer of gold in an
ion coater SPI model 11430E to provide proper surface
conduction.
Swelling measurements
Swelling properties were studied using conventional gravi-
metric procedure. The swelling behavior of dried hydrogels
was determined by immersing the completely xerogel samples
in double-distilled water at 25 °C. After wiping the excess
surface liquid with filter paper, swollen gels were weighed
on an electronic balance, at predetermined intervals of time
until the hydrogel reached constant weight. At this point, the
sample is considered to have achieved physicochemical equi-
librium or equilibrium swelling, Seq.
The swelling ratio (%S) and equilibrium water content
(EWC) was calculated using the following equation [30]:
h . i
%S ¼ ðW t –W 0 Þ W 0  100 ð1Þ
h  . i
EWC ¼ W eq −W 0 W eq  100 ð2Þ
, where Wt is the weight of swollen hydrogel at time t, and W0
is the weight of the dry gel at time 0 and Weq is the weight of
the sample swollen at equilibrium.
All swelling measurements were done by duplicate or
triplicate.
J Polym Res (2015) 22:233
Results and discussion
Synthesis of Hydrogels
AAm/IA, AAm/MEI, and AAm/DEI hydrogels were prepared
with a molar ratio of 100/0, 90/10, 80/20, and 70/30 in water
and a mixture of water/alcohol (60/40 v:v), with the aim to
determine the effect of the nature of the components, the com-
position, and the solvent media in the swelling properties. As
mentioned above, AAm/IA hydrogels have been prepared
[23, 24, 26], but there the content of IA used in the hydrogel
was significantly lower than those used in this investigation.
On the other hand, it is important to note that when the poly-
merization is carried out with a proportion of IA or itaconate
greater than 30 %, reaction doesn’t take place. Moreover,
AAm/DEI hydrogel (70/30) could not be obtained when a
mixture of water/ethanol was employed as solvent. The syn-
thesis of the hydrogels is represented schematically in Fig. 1.
The hydrogels were obtained in cylindrical forms and all
samples of AAm/IA and AAm/DEI were colorless and trans-
parent, while the AAm/MEI samples were yellowish. In most
cases, hydrogels were obtained with quantitative conversions
or in amounts slightly above 100 %. This can be attributed to
moisture retained in the network of all the hydrogels, probably
due to associated water. All TGA thermograms showed an
initial weight loss near 100 °C, which is close to the excess
weight found in the samples, corroborating the presence of
water in the samples.
The structure of these materials was studied by FTIR spec-
troscopy, and Fig. 2 displays the spectra of the series of AAm/
DEI that could be considered representative of all series.
There, the presence of the bands of both polyacrylamide
(PAAm) and poly(dimethoxyethyl itaconate) (PDEI) were ob-
served [21]. In all cases the C=C stretching signal at 1640 and
1612 cm−1 of the itaconate and acrylamide monomers are
absent, indicating that all monomeric unities are involved in
the polymerization reaction.
On the other hand, in the figure it can be observed that the
intensity of stretching vibration of the carbonyl group of DEI
Fig. 1 Schematic representation
of hydrogels synthesis
Page 3 of 10 233
moiety (1733 cm−1) increase respect to stretching vibration of
carbonyl group of Amide I (1672 cm−1) and bending vibration
N-H bond (Amide II, 1614 cm−1) of the AAm moiety when
the proportion of itaconate in the hydrogel raise.
Swelling studies
After the hydrogels were characterized, a swelling study in
water was carried out, and the results of this study indicated
that the swelling ability depends of the molar ratio of AAm/I,
the nature of the itaconate derivative, and the solvent used for
synthesis. Water absorption of hydrogels was followed as a
function of time until reaching equilibrium state, and as seen
in Fig. 3, all of them display typical swelling isotherms. In all
cases the swelling behavior is reproducible after drying the
samples and reswelling.
The values of Seq and EWC are given in Table 1. From
there it is clear that the swelling of AAm/I hydrogels is influ-
enced by three main factors: the nature of the comonomer (IA,
MEI, or DEI), their proportion in the hydrogel, and the solvent
used in the synthesis.
In all cases with the increase of the comonomer proportion
in the hydrogel, the swell ability increases, reaching a maxi-
mum value at a molar ratio of 70/30. The higher swelling
values are reached with the AAm/MEI systems, and when
they are synthesized with a molar ratio of 70/30, reach swell-
ing values up to 43,000. On the other hand, AAm/MEI and
AAm/IA systems swell much more than AAm/DEI. When the
swelling was carried out in physiological solution (0.9 %
NaCl in distilled water) instead distilled water, the behavior
was very similar.
This strongly suggests that the carboxylic acid and ester
groups are responsible for a significant increase in the swell-
ing capacity of these hydrogels relative to pure AAm hydro-
gel. However, the carboxylic acid groups have a more signif-
icant effect, probably due to the interaction with water through
hydrogen bonds and subsequent ionization of the carboxylic
groups [29–32]. As for other hydrogels that possess easily
ionized functional groups, the swelling is increased not only
233 Page 4 of 10
Fig. 2 FTIR spectra of the PDEI, PAAm, and AAm/DEI hydrogels
synthesized at different molar ratios in water as solvent
by the hydrogen bond formations, but also by the electrostatic
repulsion of the ionic charges of the carboxylate groups pres-
ent in their networks [30–33]. A higher proportion of IA or
MEI in the hydrogel raises the number of carboxylate groups
increasing the intermolecular repulsion forces which results in
the expansion of the network structure and the increase of the
free spaces suitable for swelling [34].
The solvent used in synthesis also influence the swelling
ability. Here, in all cases the hydrogel synthesized in water/
ethanol mixtures swelling more than those synthesized in wa-
ter. It is possible that the pore size of the hydrogel can be
influenced by solvent used in the synthesis or that the alcohol
could promote chain transfer during the synthesis “shorten-
ing” the chain length and increasing the water absorption ca-
pacity. Although at the moment we do not have a satisfactory
explanation for this, in our laboratory we are conducting some
experiments that allow obtaining a more conclusive results.
For comparison, in this work we investigate another system
in which the hydrogels were prepared with HEAAm instead of
AAm in order to examine the effect of the side chain and the
hydroxyl group present in the monomer in the swelling prop-
erties. The method of synthesis employed was the same used
for the AAm systems. Most of the HEAAm based hydrogels
were obtained in high yields and the IR spectra confirmed
their structure. As for the former series, the IR spectra showed
Fig. 3 Swelling curves of AAm/I 80/20 hydrogels series in distilled
water as function of time
J Polym Res (2015) 22:233
that as the itaconate proportion increases in the hydrogel, the
intensity of the vibration of its carbonyl group increases with
respect to the HEAAm one.
Swelling values of these hydrogels are shown in Tables 2
and 3, and as may seen there, the swelling behavior of these
series is different to that observed for an AAm based hydrogel.
HEAAm/IA and HEAAm/MEI hydrogels, after purification
and drying, exhibit an opposite swelling behavior to that shown
by AAm/IA and AAm/MEI. As can be appreciated, with the
increase of the comonomer proportion, the hydrogel swelling
capacity diminishes, and in all cases obtained values are lower
than those of a pure HEAAm hydrogel. However, HEAAm/
DEI shows a similar behavior to that showed by AAm series.
This apparent anomalous behavior of HEAAm/IA and
HEAAm/MEI hydrogels could be due to the complex forma-
tion between the carboxylic acid present in the IA or MEI
moiety with the hydroxyl group of the side chain of HEAAm.
The formations of complex by hydrogen bonds between
poly(carboxylic acid) with a proton-accepting nonionic poly-
mer has been reported. One example of this is the formation of
stoichiometric interpolymer complexes between poly(acrylic
acid) with poly(2-hydroxyethyl acrylate) when the proportion
of poly(2-hydroxyethyl acrylate) exceeds significantly that of
poly(acrylic acid) [35, 36]. Something similar may occur with
the HEAAm/IA and HEAAm/MEI hydrogels. Here, the ex-
cess of HEAAm allows an intramolecular complex formation
hampering the expansion of the network reducing significant-
ly the swelling capacity. This effect increases with an increase
of the amount of IA or MEI in the hydrogel as may be seen in
Tables 2 and 3.
However, when the newly synthesized hydrogels in water
are allowed to swell immediately after the synthesis, the swell-
ing behavior results are similar to that observed for an AAm
hydrogel, but after drying and re-swelling its swelling behav-
ior is as shown in Table 3.
This indicates that during the synthesis process, the forma-
tion of the complex doesn’t take place, or if it does, it hap-
pened in very little extension. This is probably because the
great amount of solvent present in the reaction media doesn’t
let the approach of the carboxylic and –OH groups and the
newly formed network reach its maximum swelling. But when
the water begins to release, the network shrinks and allows the
approximation of the hydroxyls and carboxylic groups of the
HEAAm and the AI or MEI permitting the formation of hy-
drogen bonds. Once formed the complexes, they remain and
cannot be broken when the hydrogel is placed in water once
more. Now the network is more compact and as consequence
the swelling is hindered.
The absence of carboxylic acid groups in DEI doesn’t al-
low the formation of these joints, and the HEAAm/DEI be-
havior is similar to the AAm/DEI behavior. Fig. 4 shows
schematically the interaction between a MEI and IA with
HEAAm unities.
J Polym Res (2015) 22:233 Page 5 of 10 233

Table 1 Values of swelling of hydrogels of AAm/IA, AAm/MEI, and AAm/DEI(a)

AAm/I (mol/mol) AAm/IA(b) AAm/MEI(b) AAm/DEI(b) AAm/AI(c) AAm/DEI(c)

Seq(d) (%) EWC(e) (%) Seq(d) (%) EWC(e) (%) Seq(d) (%) EWC(e) (%) Seq(d) (%) EWC(e) (%) Seq(d) (%) EWC(e) (%)

100/0 2534 96.2 2534 96.2 2402 96.0 1449 93.5 1449 93.5
90/10 11,122 99.1 18,735 99.5 3567 97.3 3664 97.3 1478 93.7
80/20 20,330 99.5 30,329 99.8 10,497 99.1 12,771 99.2 2010 95.3
70/30 37,400 99.7 43,387 99.8 –(f) –(f) 18,306 99.5 2472 96.1
a)
Synthesized at 60 °C for 24 h for AAm/AI and AAm/MEI and 48 h for AAm/DEI, using AMS as initiator (1 % molar) and MBAm as crosslinking
agent (1 % molar). b) Synthesized in water/ethanol mixture (60/40 V:V)
c)
Synthesized in water. d) Equilibrium swelling. e) Equilibrium water content. f) Polymer was not obtained

Water transport mechanisms in hydrogels
The diffusion of small molecules into the hydrogel depends on
the physical properties of the polymer network and the inter-
actions between the polymer segments with these small mol-
ecules. According to Fick’s second law, a power law equation
can be used to determine the type of water diffusion in
hydrogels [37–39].
. values were obtained [37, 38]. In Fig. 5, some representative
F ¼ W t W ∞ ¼ Kt n ð3Þ
, where F represents the power of swelling of the hydrogel, Wt
and W∞ are the mass of water absorbed at time t and at equi-
librium, respectively, K is a constant related to gel structure
and n is the swelling exponent that takes into account the
mode of water transport.
From this perspective and based on the relative rate of
water diffusion into the polymer matrix and the rate of poly-
mer chain relaxation, swelling of the system was analyzed to
establish which physical factors determine the mechanism of
penetration of water into the hydrogel. In this sense, if n≈0.50
the transport mechanism is controlled by Fickian diffusion or
case I (the diffusion rate is much lower than relaxation). When
n=1, the transport mechanism is controlled by diffusion, case
II (diffusion is fast compared to the relaxation processes).
However, a value of n between 0.50 and 1.00 means that the
transport mechanism has a non Fickian or anomalous behav-
ior, arising from the contribution of two simultaneous process-
es: diffusion phenomenon accompanied by the viscoelastic
relaxation of the polymer chains [37]. For n<0.5 the transport
mechanism can be described as Bless Fickian behavior^,
which is observed when the rate of water penetration is much
lower than the rate of relaxation of chains [35, 36].
By plotting Ln Wt / W∞ vs. Ln t for 0<Wt / W∞ <0.6, K and n
results are shown and the swelling exponents calculated from
the slopes of lines are listed in Tables 4 and 5.
As may be observed from Tables 4 and 5, most of the n
values obtained for HEAAm/IA, AAm/IA, and AAm/MEI
hydrogels ranged from 0.6 to 0.8 indicating that the transport
mechanism has a non-Fickian or anomalous behavior. Where-
as in the case of hydrogels AAm, AAm/DEI, HEAAm,
HEAAm/MEI, n values are less than 0.5, which indicates a
Bless Fickian^ behavior. This strongly suggests that the diffu-
sion coefficient values are affected by the structure of the
itaconate unit of the hydrogels. Thus, AAm/MEI and AAm/
IA show the same diffusion process, which is different when
DEI was used to synthesize these materials. This could be
explained because the carboxylic acid groups present in the
IA and MEI structure due to this type of hydrogel is more
hydrophilic, thus facilitating the entry of water by diffusion.
DEI has no such groups and, therefore, the material is less

Table 2 Values of swelling of hydrogels of HEAAm/IA, HEAAm/MEI, and HEAAm/DEI synthesized in water/ethanol mixture (60/40 V:V) (a)

HEAAM/I (mol/mol) HEAAm/IA HEAAm/MEI HEAAM/DEI

Seq(b) (%) EWC(c) (%) Seq(b) (%) EWC(c) (%) Seq(b) (%) EWC(c) (%)

100/0 2104 95.5 2223 95.7 2223 95.7

90/10 702 87.5 426 81.0 2601 96.4
80/20 678 87.2 320 76.2 2742 96.5
70/30 582 84.8 216 68.4 3300 97.1
a) b) c)
Synthesized at 60 °C for 24 h, using AMS as initiator (1 % molar) and MBAm as crosslinking agent (1 % molar). Equilibrium swelling.
Equilibrium water content
233 Page 6 of 10 J Polym Res (2015) 22:233

Table 3 Values of swelling of HEAAM/IA and HEAAM/MEI hydrogels synthesized in water (a)

HEAAM/I (mol/mol) HEAAm/IA HEAAm/MEI

After purification Newly synthesized After purification Newly synthetized

Seq(b) (%) EWC(c) (%) Seq(b) (%) EWC(c) (%) Seq(b) (%) EWC(c) (%) Seq(b) (%) EWC(c) (%)

100/0 1564 94.0 3414 97.2 1501 93.7 3414 97.2

90/10 688 87.3 11,035 99.1 519 88.4 5500 98.2
80/20 444 81.6 13,526 99.3 303 75.2 6554 98.5
70/30 434 78.1 39,952 99.8 259 72.0 6893 98.6
a) b) c)
Synthesized at 60 °C for 24 h, using AMS as initiator (1 % molar) and MBAm as crosslinking agent (1 % molar). Equilibrium swelling.
Equilibrium water content

hydrophilic hindering the water inlet to the network. Then, in
this case the relaxation process prevails over diffusion. The
HEAAm/MEI hydrogels exhibit an abrupt change with re-
spect to the AAm/MEI hydrogels; this may be attributed to
interactions between the internal-OH groups present in the
monomeric unit HEAAm, which prevent inlet of the water
by easy diffusion.
All these results indicate that the diffusion properties can be
controlled by adjusting in an appropriate manner the compo-
sition and structure of the comonomeric units during the hy-
drogel synthesis.
Morphological analysis
The morphology of these hydrogels was studied by scanning
electron microscopy, and the micrographs of some samples
derivatives of AAm and HEAAm hydrogels, which can be
considered representative of the whole series are shown in
Fig. 6. In all cases, it can be seen that all samples are consti-
tuted by porous materials where the pore size and appearance
of the samples are different depending on the constitution of
the sample. For example, Fig. 6a, b, and c correspond to pure
AAm, AAm/IA 90/10, and AAm/MEI 90/10, and there it can
be observed that for the last two micrographs, the pore size is
larger and deeper compared to a pure AAm hydrogel. This
reflects a higher capacity of water absorption of AAm/IA
and AAm/MEI hydrogels with respect to an AAm hydrogel.
It is also possible that the higher capacity of the copolymer to
form larger size pores, together with the specific hydrophilic
interactions that the carbonyl group is able to form with water,
contribute to an increase in the swelling capacity of these
materials. At this point it is worth mentioning that for samples
of AAm/IA and AAm/MEI with a molar ratio of 70/30 it was
not possible to observe any morphology by SEM, possibly
because the large structural deformation due to the large swell-
ing which was submitted.
Figure 6d corresponds to the pure HEAAm hydrogel,
whereas Fig. 6e and f to HEAAm/AI 80/20, the former to a
sample washed, dried, and swollen again to equilibrium, and
the last one to a sample swollen to equilibrium without first
drying the sample. The three samples do not show very sig-
nificant differences in the pore size. However, purified
HEAAm and HEAAm/AI exhibit a similar morphology
where the pores are shallow at a difference of the AAm
hydrogels, which, as previously motioned, show deep pores.
Meanwhile, for the HEAAm/IA sample swollen without pre-
vious purification or drying, shape, and depth of the pore is
more like the AAm/IA and AAm/MEI hydrogel. Moreover,
the swelling reached for an HEAAm/AI sample swollen with-
out previous purification is quite similar to AAm/IA 80/20 and
much larger than purified AAm, HEAAm, and HEAAm/IA.
This allows us to conclude that the size and mainly the depth
of the pores are related to the capacity of swelling. The swell-
ing behavior of HEAAm before and after purification and
drying as already explained is due to the interaction between
the hydroxyl of the side chain of the HEAAm with the

Fig. 4 Schematic representation

of the interaction between
HEAAm unities with: (a) MEI
and (b) IA
J Polym Res (2015) 22:233 Page 7 of 10 233

Table 5 Swelling exponents (n) and swelling constants (K) of

HEAAm/I hydrogels

HEAAm/IA (mol/mol) 100/0 90/10 80/20 70/30

n 0.48 0.65 0.60 0.63
K×103 28.30 14.30 17.40 19.20
HEAAm/MEI (mol/mol) 100/0 90/10 80/20 70/30
n 0.48 0.30 0.20 0.13
K×103 28.30 145.20 217.50 300.80
HEAAm/DEI (mol/mol) 100/0 90/10 80/20 70/30
n 0.48 0,45 0.45 0,44
K×103 28.3 22.90 22.60 18.10

Fig. 5 Zero order swelling kinetics in the initial phase of swelling to

hydrogels (series AAm/I 80/20)
which is close to the first degradation stage happened for both
homopolymers [21]. The amount of weight loss in this stage is
carbonyl groups, which hamper the expansion of the network about 29 %. This value is close enough to 32.4 %, which is the
and possibly modifying the structure and the morphology as expected for the weight loss of the total ammonia and 2-
can be appreciated in the micrographs. metoxyethanol released of a combined degradation process of
PAAm and PMEI in a molar ratio 70/30. This strongly suggests
Thermal stability that the hydrogel degradation process may be a combination of
those that take place in the respective homopolymers.
The thermal stability of the AAM/I hydrogel was studied by In order to confirm this, an analysis by TVA was carried
TGA. In Fig. 7 are shown the thermograms of AAm/MEI and out. Samples were heated to a temperature near 350 °C to
AAm/DEI 70/30 hydrogels, which may be considered as rep- examine the volatiles produced during the degradation pro-
resentative of the whole series. The mechanisms of degrada- cess. The FTIR spectrum of the volatile liquid fraction con-
tion of both PAAm and poly(itaconates) are well known. densing at room temperature indicates that it was mainly con-
PAAm is stable to about 200 °C and the degradation occurs stituted of 2-methoxy ethanol. The alcohol is produced by the
in two stages, where in the first one, the major degradation anhydride formation due the attack of the carboxylic acid to
product is ammonia [40]. The degradation of poly(monoalkyl the ester of an itaconate unit, with the release of the side chain
itaconates) also occurs in two stages: the first step, starting at as an alcohol molecule. Because of the low itaconate propor-
temperatures near 100 °C, the formation of anhydrides with tion in the hydrogel, it would be probably that the reaction
corresponding loss of the side chain as alcohol molecule oc- take place in the same monomer unit allowing the formation
curs [41], whereas poly(diitaconates) begins to degrade over of 5-member cyclic anhydride [21].
200 °C, mainly through a depolymerization process [42, 43]. In the fraction condensed in the gas cell, at liquid nitrogen
As it may be appreciated in Fig. 7a, TGA and DTGA show temperature, CO2, NH3, and CO was detected. The CO2 pro-
that degradation process of AAm/MEI hydrogel occur in two ceeds from the itaconate moiety degradation and is confirmed
main stages. The first stage beginning near 150 °C just like by the presence of a strong band that appears at 2359 cm−1.
PMEI does and the process takes place in a temperature range, Meanwhile, the NH3 is the main product of the degradation of
PAAm moiety and its presence is confirmed by the 3300 and
1010 cm−1 bands. CO (2170 and 2120 cm−1) is a degradation
Table 4 Swelling exponents (n) and swelling constants (K) of AAm/I product of both components [21].
hydrogels
The AAm/DEI (Fig. 7b) begins to degrade at 200 °C, as it
AAm/IA (mol/mol) 100/0 90/10 80/20 70/30 happened for PAAm. Because of the low proportion of the
n 0.44 0.66 0.64 0.65 itaconate unit and as they are randomly distributed in the
K×103 30.50 7.20 3.60 2.20 polymer, depolymerization reaction of the diitaconate is not
AAm/MEI (mol/mol) 100/0 90/10 80/20 70/30 able to occur, at least to a detectable extent, because the im-
n 0.44 0.80 1.10 0.80 probable formation of appreciable sequences of DEI units
K×103 30.50 3.50 0.80 1.30 [44]. Therefore, the degradation process will not begin until
AAm/DEI (mol/mol) 100/0 90/10 80/20 70/30 the degradation temperature of the PAAm moieties is reaches.
n 0.44 0.37 0.45 – The volatiles fraction collected by TVA heating near 300 °C
K×103 30.5 22.80 9.80 – also shows the presence of CO2, NH3 , and CO. The presence
of DEI (monomer) or small fractions of PDEI was not
233 Page 8 of 10 J Polym Res (2015) 22:233

Fig. 6 SEM micrographs of a) AAm; b) AAm/AI 90/10; c) AAm/MEI 90/10, d) HEAAM; e) HEAAM/AI 80/20 after the purification procedure (see
Synthesis of hydrogels section) and swelling again; f) HEAAM/AI 80/20 swollen immediately after synthesis without purification and drying

observed, confirming that the depolymerization reaction of the must take place by the release of the side chains of DEI unit,
diitaconate is not able to occur. However, some amount of 2- probably by an intramolecular reaction to form five-member
methoxyethanol was detected. The formation of the alcohol cyclic anhydrides, which is favored by the temperature [44].

Fig. 7 TGA (a) and DTGA (b) traces of hydrogels: AAm/MEI 70/30 (A) and AAm/DEI 70/30 (B)
J Polym Res (2015) 22:233
Conclusions
The method of synthesis presented here allowed obtaining two
series of hydrogels of AAm and HEAAm with IA or itaconates
(I) in various compositions. In most cases, almost quantitative
yields were obtained. Hydrogel systems swelled in the range
2000–43,000 %. The higher swelling values were reaching
with the AAm/MEI systems, and when they were synthetized
with a molar ratio of 70/30. On the other hand, AAm/MEI and
AAm/IA systems swell much more than AAm/DEI and
HEAAm systems. In the case of AAm/I hydrogel, swelling
ability increases when comonomer proportion increase. This
shows that the carboxilic acid group presents in IA and MEI
were the main responsible of the swelling. However in the
HEAAm/IA and HEAAm/MEI systems the swelling behavior
is contrary to the showed by AAm/MEI and AAm/IA
hydrogels. It can be due to the complex formation between
the carboxylic acid present in the IA or MEI moiety with the
hydroxyl group of the side chain of HEAAm. TGA indicate
that AAm/MEI hydrogels are thermally stable up to 150 °C,
while AAm/DEI begins to lose weight near 200 °C. TVA re-
sults suggest that the whole degradation takes place as a com-
bination of the degradation of the both components.
High hydrophilic HEAAm/IA, AAm/IA, and AAm/MEI
hydrogels follow a non-Fickian mechanism with n values be-
tween 0.6 and 0.8, whereas less hydrophilic hydrogels as
AAm, AAm/DEI, HEAAm, HEAAm/DEI HEAAm/MEI fol-
low a Bless Fickian^ behavior process.
In the morphological analysis it was observed that all sam-
ples are constituted by porous materials where the pore size
and appearance of the samples are different depending of the
constitution of the sample. Thus, for the hydrogel AAm/I, the
morphological surface it has larger pores and deep than the
system HEAAm/I.
Acknowledgments The authors gratefully acknowledge the financial
support of CONSEJO de DESARROLLO CIENTÍFICO
HUMANÍSTICO y TECNOLÓGICO DE LA UNIVERSIDAD DE
LOS ANDES, Mérida (Venezuela) (CDCHT-ULA) through grant num-
bers C-1746-1108-B.
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