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DOI 10.1007/s10965-015-0876-2
ORIGINAL PAPER
Synthesis of hydrogels was carried out in water or in a water/ Swelling properties were studied using conventional gravi-
ethanol 60/40 (V/V) mixture, using APS as initiator and metric procedure. The swelling behavior of dried hydrogels
MBAM as crosslinking agent both 1 % respect to the total was determined by immersing the completely xerogel samples
moles of comonomers. The synthesis was performed accord- in double-distilled water at 25 °C. After wiping the excess
ing the following procedure: Predetermined amounts of co- surface liquid with filter paper, swollen gels were weighed
monomers (AAm or HEAAm together IA, MEI, or DEI) were on an electronic balance, at predetermined intervals of time
dissolved in the chosen solvent (water or water/ethanol 60/40 until the hydrogel reached constant weight. At this point, the
V/V) in a glass tube (A). In another tube (B), amounts required sample is considered to have achieved physicochemical equi-
of the initiator and crosslinking agent were dissolved in 2 mL librium or equilibrium swelling, Seq.
of the same solvent used to prepare solution A. This solution The swelling ratio (%S) and equilibrium water content
was added into the tube A. Then the reaction mixture was (EWC) was calculated using the following equation [30]:
purged with nitrogen gas for 5 min to eliminate dissolved h . i
oxygen, and the reaction tubes were placed in a thermostatic %S ¼ ðW t –W 0 Þ W 0 100 ð1Þ
bath at 60 °C for 24 or 48 h. At the end of the polymerization, h . i
the hydrogels were taken out by breaking the glass tubes. EWC ¼ W eq −W 0 W eq 100 ð2Þ
Fresh hydrogels obtained in long cylindrical shapes were cut
into fine pellets, and were washed several times with the sol- , where Wt is the weight of swollen hydrogel at time t, and W0
vent used in the synthesis. Finally, the hydrogels were air- is the weight of the dry gel at time 0 and Weq is the weight of
dried at room temperature for several days until constant the sample swollen at equilibrium.
weight. The hydrogel chemical structure was confirmed by All swelling measurements were done by duplicate or
FTIR spectroscopy. triplicate.
J Polym Res (2015) 22:233 Page 3 of 10 233
Results and discussion moiety (1733 cm−1) increase respect to stretching vibration of
carbonyl group of Amide I (1672 cm−1) and bending vibration
Synthesis of Hydrogels N-H bond (Amide II, 1614 cm−1) of the AAm moiety when
the proportion of itaconate in the hydrogel raise.
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 Swelling studies
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- After the hydrogels were characterized, a swelling study in
position, and the solvent media in the swelling properties. As water was carried out, and the results of this study indicated
mentioned above, AAm/IA hydrogels have been prepared that the swelling ability depends of the molar ratio of AAm/I,
[23, 24, 26], but there the content of IA used in the hydrogel the nature of the itaconate derivative, and the solvent used for
was significantly lower than those used in this investigation. synthesis. Water absorption of hydrogels was followed as a
On the other hand, it is important to note that when the poly- function of time until reaching equilibrium state, and as seen
merization is carried out with a proportion of IA or itaconate in Fig. 3, all of them display typical swelling isotherms. In all
greater than 30 %, reaction doesn’t take place. Moreover, cases the swelling behavior is reproducible after drying the
AAm/DEI hydrogel (70/30) could not be obtained when a samples and reswelling.
mixture of water/ethanol was employed as solvent. The syn- The values of Seq and EWC are given in Table 1. From
thesis of the hydrogels is represented schematically in Fig. 1. there it is clear that the swelling of AAm/I hydrogels is influ-
The hydrogels were obtained in cylindrical forms and all enced by three main factors: the nature of the comonomer (IA,
samples of AAm/IA and AAm/DEI were colorless and trans- MEI, or DEI), their proportion in the hydrogel, and the solvent
parent, while the AAm/MEI samples were yellowish. In most used in the synthesis.
cases, hydrogels were obtained with quantitative conversions In all cases with the increase of the comonomer proportion
or in amounts slightly above 100 %. This can be attributed to in the hydrogel, the swell ability increases, reaching a maxi-
moisture retained in the network of all the hydrogels, probably mum value at a molar ratio of 70/30. The higher swelling
due to associated water. All TGA thermograms showed an values are reached with the AAm/MEI systems, and when
initial weight loss near 100 °C, which is close to the excess they are synthesized with a molar ratio of 70/30, reach swell-
weight found in the samples, corroborating the presence of ing values up to 43,000. On the other hand, AAm/MEI and
water in the samples. AAm/IA systems swell much more than AAm/DEI. When the
The structure of these materials was studied by FTIR spec- swelling was carried out in physiological solution (0.9 %
troscopy, and Fig. 2 displays the spectra of the series of AAm/ NaCl in distilled water) instead distilled water, the behavior
DEI that could be considered representative of all series. was very similar.
There, the presence of the bands of both polyacrylamide This strongly suggests that the carboxylic acid and ester
(PAAm) and poly(dimethoxyethyl itaconate) (PDEI) were ob- groups are responsible for a significant increase in the swell-
served [21]. In all cases the C=C stretching signal at 1640 and ing capacity of these hydrogels relative to pure AAm hydro-
1612 cm−1 of the itaconate and acrylamide monomers are gel. However, the carboxylic acid groups have a more signif-
absent, indicating that all monomeric unities are involved in icant effect, probably due to the interaction with water through
the polymerization reaction. hydrogen bonds and subsequent ionization of the carboxylic
On the other hand, in the figure it can be observed that the groups [29–32]. As for other hydrogels that possess easily
intensity of stretching vibration of the carbonyl group of DEI ionized functional groups, the swelling is increased not only
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 transport mechanism has a non Fickian or anomalous behav-
ior, arising from the contribution of two simultaneous process-
The diffusion of small molecules into the hydrogel depends on es: diffusion phenomenon accompanied by the viscoelastic
the physical properties of the polymer network and the inter- relaxation of the polymer chains [37]. For n<0.5 the transport
actions between the polymer segments with these small mol- mechanism can be described as Bless Fickian behavior^,
ecules. According to Fick’s second law, a power law equation which is observed when the rate of water penetration is much
can be used to determine the type of water diffusion in lower than the rate of relaxation of chains [35, 36].
hydrogels [37–39]. By plotting Ln Wt / W∞ vs. Ln t for 0<Wt / W∞ <0.6, K and n
. values were obtained [37, 38]. In Fig. 5, some representative
F ¼ W t W ∞ ¼ Kt n ð3Þ results are shown and the swelling exponents calculated from
the slopes of lines are listed in Tables 4 and 5.
, where F represents the power of swelling of the hydrogel, Wt As may be observed from Tables 4 and 5, most of the n
and W∞ are the mass of water absorbed at time t and at equi- values obtained for HEAAm/IA, AAm/IA, and AAm/MEI
librium, respectively, K is a constant related to gel structure hydrogels ranged from 0.6 to 0.8 indicating that the transport
and n is the swelling exponent that takes into account the mechanism has a non-Fickian or anomalous behavior. Where-
mode of water transport. as in the case of hydrogels AAm, AAm/DEI, HEAAm,
From this perspective and based on the relative rate of HEAAm/MEI, n values are less than 0.5, which indicates a
water diffusion into the polymer matrix and the rate of poly- Bless Fickian^ behavior. This strongly suggests that the diffu-
mer chain relaxation, swelling of the system was analyzed to sion coefficient values are affected by the structure of the
establish which physical factors determine the mechanism of itaconate unit of the hydrogels. Thus, AAm/MEI and AAm/
penetration of water into the hydrogel. In this sense, if n≈0.50 IA show the same diffusion process, which is different when
the transport mechanism is controlled by Fickian diffusion or DEI was used to synthesize these materials. This could be
case I (the diffusion rate is much lower than relaxation). When explained because the carboxylic acid groups present in the
n=1, the transport mechanism is controlled by diffusion, case IA and MEI structure due to this type of hydrogel is more
II (diffusion is fast compared to the relaxation processes). hydrophilic, thus facilitating the entry of water by diffusion.
However, a value of n between 0.50 and 1.00 means that the 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)
Seq(b) (%) EWC(c) (%) Seq(b) (%) EWC(c) (%) Seq(b) (%) EWC(c) (%)
Table 3 Values of swelling of HEAAM/IA and HEAAM/MEI hydrogels synthesized in water (a)
Seq(b) (%) EWC(c) (%) Seq(b) (%) EWC(c) (%) Seq(b) (%) EWC(c) (%) Seq(b) (%) EWC(c) (%)
hydrophilic hindering the water inlet to the network. Then, in form larger size pores, together with the specific hydrophilic
this case the relaxation process prevails over diffusion. The interactions that the carbonyl group is able to form with water,
HEAAm/MEI hydrogels exhibit an abrupt change with re- contribute to an increase in the swelling capacity of these
spect to the AAm/MEI hydrogels; this may be attributed to materials. At this point it is worth mentioning that for samples
interactions between the internal-OH groups present in the of AAm/IA and AAm/MEI with a molar ratio of 70/30 it was
monomeric unit HEAAm, which prevent inlet of the water not possible to observe any morphology by SEM, possibly
by easy diffusion. because the large structural deformation due to the large swell-
All these results indicate that the diffusion properties can be ing which was submitted.
controlled by adjusting in an appropriate manner the compo- Figure 6d corresponds to the pure HEAAm hydrogel,
sition and structure of the comonomeric units during the hy- whereas Fig. 6e and f to HEAAm/AI 80/20, the former to a
drogel synthesis. sample washed, dried, and swollen again to equilibrium, and
the last one to a sample swollen to equilibrium without first
Morphological analysis drying the sample. The three samples do not show very sig-
nificant differences in the pore size. However, purified
The morphology of these hydrogels was studied by scanning HEAAm and HEAAm/AI exhibit a similar morphology
electron microscopy, and the micrographs of some samples where the pores are shallow at a difference of the AAm
derivatives of AAm and HEAAm hydrogels, which can be hydrogels, which, as previously motioned, show deep pores.
considered representative of the whole series are shown in Meanwhile, for the HEAAm/IA sample swollen without pre-
Fig. 6. In all cases, it can be seen that all samples are consti- vious purification or drying, shape, and depth of the pore is
tuted by porous materials where the pore size and appearance more like the AAm/IA and AAm/MEI hydrogel. Moreover,
of the samples are different depending on the constitution of the swelling reached for an HEAAm/AI sample swollen with-
the sample. For example, Fig. 6a, b, and c correspond to pure out previous purification is quite similar to AAm/IA 80/20 and
AAm, AAm/IA 90/10, and AAm/MEI 90/10, and there it can much larger than purified AAm, HEAAm, and HEAAm/IA.
be observed that for the last two micrographs, the pore size is This allows us to conclude that the size and mainly the depth
larger and deeper compared to a pure AAm hydrogel. This of the pores are related to the capacity of swelling. The swell-
reflects a higher capacity of water absorption of AAm/IA ing behavior of HEAAm before and after purification and
and AAm/MEI hydrogels with respect to an AAm hydrogel. drying as already explained is due to the interaction between
It is also possible that the higher capacity of the copolymer to the hydroxyl of the side chain of the HEAAm with the
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 Page 9 of 10 233
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