ISSN 1061933X, Colloid Journal, 2012, Vol. 74, No. 6, pp. 645648. Pleiades Publishing, Ltd., 2012.

Original Russian Text V.Yu. Baranovskii, V.G. Ganev, V.B. Petkova, Kh.Ch. Voicheva, M.V. Dimitrov, 2012, published in Kolloidnyi Zhurnal, 2012, Vol. 74, No. 6, pp. 675679.

Hydrogels Based on Polycarboxylic AcidAgarAgar Complexes

V. Yu. Baranovskiia, V. G. Ganeva, V. B. Petkovab, Kh. Ch. Voichevaa, and M. V. Dimitrovb
a
Institute of Polymers, Bulgarian Academy of Sciences, ul. Akad. G. Bonchev 103, Sofia, 1113 Bulgaria
b
Sofia Medical University, Pharmaceutical Department, ul. Dunav 2, Sofia, 1000 Bulgaria
Received December 19, 2011

AbstractIR spectroscopy and viscometry data have shown that poly(acrylic acid) and poly(methacrylic
acid) form complexes with agaragar in aqueous solutions as they do with other polysaccharides. The poly
acidagaragar complexes are typical hydrogels. The swelling index of hydrogels based on the poly(meth
acrylic acid)agaragar complex has been found to be markedly lower than that of poly(acrylic acid)agar
agar complex. The hydrogels based on the complex of crosslinked poly(acrylic acid) with agaragar can be
of practical interest as polymeric carriers for drugs.
DOI: 10.1134/S1061933X12060026

INTRODUCTION The AA macromolecule contains up to 80% of aga

Agaragar (AA) hydrogels are widely applied in rosea linear polysaccharide consisting of alternat
various fields of human activity, e.g., in the light and ing residues of 30substituted Dgalactopyranose
food industries, agriculture, biotechnology, microbi and 40substituted 3,6anhydroLgalactopyra
ology, pharmacology, medicine, etc. nose:

OH O
OH
CH2 H CH2 H H
OH O O
OH H O H O
CH2 H CH2 H H O 1
O
O H O 1 O 3 H OH 1
4 H
H OH
O H H H
O 4 O
3 H OH 1 H
OH
H H H

AA dissolves in water at 8385C with the forma
tion of a true solution. Subsequent cooling of a solu
tion with a concentration above 0.5% to 3540C
gives rise to a hydrogel.
The sources of AA are red and brown see algae; i.e.,
AA is a renewable natural substance.
By its chemical structure, AA belongs to the class of
polysaccharides. There are numerous reports devoted
to the investigation of the complexation of polysac
charides with polycarboxylic acids, namely,
poly(acrylic acid) (PAA) and poly(methacrylic acid)
(PMAA), in aqueous solutions (see, e.g., [115]). Var
ious cellulose derivatives, such as methyl [15],
hydroxyethyl [68], hydroxypropyl [913], and
hydroxypropylmethylcellulose [14, 15], are mainly
used as polysaccharides. The physicochemical proper
ties of the resulting complexes have been studied as
functions of medium pH and temperature, reagent
concentrations, and ionic strength of solutions. In
most cases, the complexes have a nonstoichiometric
composition.
Being a polysaccharide, AA must also form com
plexes with PAA and PMAA. However, there are no
data in the literature on the interaction of AA with the
above polyacids in aqueous solutions. Therefore, the
goal of this work is to study the complexation of AA
with PAA and PMAA in aqueous media.
EXPERIMENTAL
PAA and PMAA were obtained by heterogeneous
polymerization of the corresponding monomers in
toluene under nitrogen at 60C using AIBN as an ini
tiator. Residual monomers were washed off with tolu
ene. The resulting polyacids were dried in vacuum at
70C to a constant weight. The molecular masses of
the polymers thus obtained were determined by vis
cometry. For PAA, [] = (1.05 103) 0.54 in 2N
NaOH at 25C [16] and, for PMAA, [] = (6.6
10 4)M 0.5 in 0.002 N HCl at 30C [17]. According to
the viscometry data, = 2.3 105 and = 9 104
for PAA and PMAA, respectively.

645
646 BARANOVSKII et al.
sp
0.09
1 the same way as in the case of the hydrogel of the
0.08
2
0.07
0.06 3 eter using samples pelleted with KBr. Differential
0.05
0.04
0.03
0.02
0.01
0 0.5 1.0 1.5 2.0
= [AA]/[PA]
Fig. 1. Dependences of specific viscosity sp on for
mixed aqueous solutions of (1) PAA with AA and
(2) PMAA with AA and (3) aqueous solution of free AA at
CPA = 0.01 g/L and 25.
AA (for microbiological purposes, Fluka) was used
as received.
The interaction between the polyacids and AA was
studied in dilute aqueous solutions. AA concentration
was no higher than 0.02% to exclude gelation. The vis
cometric measurements were performed using an
Ubbelohde capillary viscometer with a thermostating
accuracy of 0.1.
AApolyacid complexes were obtained by mixing
equal volumes of aqueous 2% solutions of the compo
nents at 8590. At this temperature, an aqueous
AA + polyacid mixed solution represented a homoge
neous transparent system. Subsequent cooling to
room temperature yielded a hydrogel, which was dried
at 60C to a constant weight. An individual AA hydro
gel was obtained through AA dissolution in water at
8590C followed by cooling to room temperature. To
estimate swelling indices Q, dried samples of the com
plexes were placed into aqueous solutions with
required pH values. The Q value was calculated by the
formula Q = (m m0)/m0, where m and m0 are the
masses of a sample swollen to the equilibrium state and
an initial dry complex, respectively.
Hydrogels based on crosslinked PAA and AA were
obtained by redox polymerization of acrylic acid
(AAc) in aqueous solutions of AA at 85C using N,N
methylenebisacrylamide (MBAA) as a crosslinking
agent and (NH4)2S2O8 + Na2S2O5 as a redox initiator.
Reaction mixtures of the following compositions were
applied: (1) 20 mL 2 + 1 g AA + 1 mL AAc + 0.1 g
MBAA + 0.005 g (NH4)2S2O8 + 0.005 g Na2S2O5 and
(2) 20 mL 2 + 1 g AA + 1 mL AAc +0.05 g
MBAA + 0.005 g (NH4)2S2O8 + 0.005 g Na2S2O5.
The compositions of both of the reaction mixtures dif
fered only in the content of the crosslinking agent: in
mixture 2, MBAA concentration was half that in
mixture 1. Resulting hydrogels were repeatedly
washed with distilled water and dried at 60C to a con
stant weight. Swelling indices Q were determined in
PAA/AA complex.
IR spectra were measured with a Bruker spectrom
spectra were obtained by subtracting the IR spectrum
of AA from the IR spectra of PMAA/AA or PAA/AA
complexes.
RESULTS AND DISCUSSION
Figure 1 shows the dependences of specific viscos
ity sp of aqueous mixed solutions of AA with PAA and
PMAA at a constant concentration of a polyacid (PA)
on the = [AA]/[PA], mass/mass, ratio, where [AA]
is the mass concentration of AA and [PA] = const =
0.01 g/dL. At low AA concentrations, the system
forms true solutions without gelation.
The incorporation of AA macromolecules into a
solution of a free PA leads to a decrease in solution sp.
This effect results from the formation of PAAA com
plex particles, which have a more compact conforma
tion than initial PAA or PMAA macromolecules have.
The compaction of the complex particles is caused by
the formation of hydrogen bonds between COOH
groups of a PA and OH groups of AA and, as a conse
quence, the hydrophobization of the interaction prod
uct.
The value of that corresponds to the minimum of
the sp() dependence is in consistence with the com
position of a PA/AA complex. However, at this value
of , the number of hydrogen bonds between COOH
groups of a polyacid and OH groups of AA in the com
plex is far from maximum. This is reasonable, because
there are substantial steric hindrances for the forma
tion of maximum possible number of hydrogen bonds.
It is essential only that the observed sp dependence
indicates the fact of the complexation between the
polyacids and AA.
An increase in sp is associated with the accumula
tion of free, uncomplexed AA macromolecules in the
solutions. This is supported by the concentration
dependence of sp for solutions of free AA.
Thus, the viscometry data show that AA forms
complexes with PAA and PMAA in aqueous solutions.
Figure 2 demonstrates the IR spectra of (1) PAA
and (2) PMAA, as well as the differential IR spectra of
(3) PAA/AA and (4) PMAA/AA complexes relative to
the spectrum of free AA. As can be seen from the com
parison of spectra 1 and 3, the absorption band at
1711 cm1, which corresponds to the stretching vibra
tions C=O in free PAA, shifts to 1736 cm1 upon its
complexation with AA. The highfrequency shift of
the stretching vibration bands C=O in the IR spectra of
PAA and PMAA upon complexation with polysaccha
rides is explained as follows. The formation of a chem
ical (covalent or hydrogen) bond between the func
tional groups of interacting polymers increases the
energy required for the excitation of stretching vibra
COLLOID JOURNAL Vol. 74 No. 6 2012