ARTICLE

pubs.acs.org/IECR

Effects of Pore-Forming Agents and Polymer Composition on the

Properties of Novel Poly(N,N-Dimethylaminoethyl Methacrylate
Sulfate-co-N,N-dimethylacrylamide) Hydrogels
G€ulten G€urdag* and Ays- eg€ul G€okalp
Department of Chemical Engineering, Faculty of Engineering, Istanbul University, 34320, Avcilar, Istanbul, Turkey

ABSTRACT: Homopolymer of N,N-dimethylaminoethyl methacrylate sulfate (DMAEMASA) and its copolymer with N,N-
dimethylacrylamide (DMAm) [P(DMAEMASA-co-DMAm)] were synthesized in the presence and absence of pore-forming agents
NaHCO3, poly(ethylene glycol) 2000 (PEG), and sucrose (SUC). The polymers were characterized by equilibrium swelling
measurements (ESVs) in distilled water (20
60 °C) and buffer solutions (I = 0.1 M, pH = 2.2
10.0, 20 °C), FTIR, DSC, and SEM
methods. The presence of DMAm in monomer feed and the use of pore-forming agents during the polymerization enhanced the
swelling of polymers. ESVs of both porous and nonporous PDMAEMASA and P(DMAEMASA-co-DMAm) gels decreased with
pH, and displayed a phase transition at pH = 5. Among the pore-formers, NaHCO3 made the highest contribution to the swelling of
polymers, but poly(ethylene glycol) and sucrose slightly affected the swelling values of gels. While glass transition temperature (Tg)
of nonporous DMAEMASA homopolymer was determined to be 168.4 °C, Tgs of nonporous copolymer with 20- and 40-mol %
DMAm were found to be 154.5 and 147.8 °C, respectively. Pore-formers decreased the Tg of homopolymer in the order NaHCO3 <
PEG < SUC. In case of copolymers, NaHCO3 and PEG had nearly no effect on Tgs, but sucrose led to approximately 7 °C decrease
in Tgs of copolymers.

1. INTRODUCTION increased the swelling values, it led to decrease in the compres-

Hydrogels are three-dimensional cross-linked hydrophilic
polymers, and they absorb large amounts of water depending
on their chemical structure (hydrophilic or hydrophobic) and
cross-link density. Smart hydogels respond to external stimuli
such as temperature, pH, ionic strength, and electric/magnetic
field, etc., as a reversible phase transition (swelling or shrinking).
These kinds of materials are finding applications in many fields
such as drug delivery,1 separation processes,2 enzyme immobili-
zation,3 and chemical sensor,4 etc. The response rate of a non-
porous gel to any stimuli is slow, and it depends on the size,
porosity, and cross-link density of the gel. The response rate can
be increased minimizing the size of the gel since the diffusion
length of water is shortened. An alternative method to obtain fast
response is to create porosity in the gel. Porous gels absorb faster
and more water than nonporous gels since in the swelling of
nonporous gels, the rate-determining step is the diffusion of
water into the polymer gel. Porous gels contain open and
interconnected pores; in the swelling of these gels, the capillary
effect has more dominant effect than the diffusion of water. They
can be prepared by methods such as porogen leaching, phase
separation, particulate cross-linking, and freeze-drying. In the
porogen leaching technique,5 porous hydrogels are prepared in
the presence of dispersed water-soluble pore-forming agents,
such as sodium chloride, PEG, and sucrose which can be
removed by washing with water during the purificiation. In a
previous work,6 we have prepared porous copolymer gels from
N-isopropylacrylamide (NIPAM) and N-hydroxymethyl acryla-
mide (NHMAAM) by using poly(ethylene glycol) 400 and 2000
(PEG 400 or PEG 2000) as pore-forming agents. While the use
of pore-forming agents PEG 400 and PEG 2000 during the
polymer synthesis favored the formation of porous gels and
sive elastic moduli of PNIPAM and P(NIPAM-co-NHMAAM)
gels. Yıldız et al.7 used PEG 4000 as porosity generator in order to
enhance the thermosensitivity of P(NIPAM-co-N-hydroxy-
methyl acrylamide) (P(NIPAM-co-NHMAAM)) gel, but it
had no effect on the shrinking rate due to the dominant effect
of skin formation during the collapse of P(NIPAM-co-
NHMAAM) gel. Kabiri et al.8 reported that acetone and sodium
bicarbonate enhanced the swelling rate of superabsorbent hydro-
gel from partially neutralized acrylic acid as high as 43
55% and
111
131%, respectively. In addition, they8 also observed that the
time and sequence of addition of the porogens, as well as the
gelation time of the polymerization, determined the efficiency of
the porogens. Lee and Yeh9 used CaCO3 and poly(ethylene
glycol) 8000 (PEG 8000) as porogen in the emulsion polymer-
ization of N-isopropylacrylamide (NIPAM) with hydrophobic
monomers such as 2,2,3,3,4,4,5,5-octafluoropentyI methacrylate
(OFPMA) and n-butyl methacrylate and determined that
CaCO3 is a more efficient pore-former than PEG 8000. For
the preparation of macroporous PNIPAM gels, the use of
aqueous solution of sucrose as polymerization medium instead
of water was reported by Zhang et al.10 Lee and Chiu11 reported
that the increase in molecular weight of poly(ethylene glycol)
gave porous PNIPAM copolymer gels with larger pore sizes.
C-aykara et al.12 synthesized thermoresponsive poly(2-diethyla-
mino ethylmethacrylate-co-N,N0 -dimethylacrylamide) gels in
the presence of NaHCO3 as porogen, and determined that ESVs
Received: November 22, 2010
Accepted: May 25, 2011
Revised: May 19, 2011
Published: May 25, 2011

r 2011 American Chemical Society 8295 dx.doi.org/10.1021/ie102349p | Ind. Eng. Chem. Res. 2011, 50, 8295–8303
Industrial & Engineering Chemistry Research ARTICLE

of gels increased with the use of NaHCO3 as pore-former and Table 1. Polymer Codes and Feed Compositions of Porous
DMAm content of copolymer. and Non-porous DMAEMASA and DMAEMASA-DMAm
Very little has been published on the polymerization of Gels
DMAEMASA13,14 monomer, in contrast to those published on
DMAEMASA DMAm pore-formera NMBAb
N,N0 -dimethylaminoethyl methacrylate (DMAEMA) polymeriza-
tion. Bune et al.13 copolymerized DMAEMASA with acrylamide polymer code (mol %) (mol %) (wt %) (mol %)
(AAM), and determined the reactivity ratios to be rDMAEMASA = 60DESA 60 40 1
1.9 ( 0.2 and rAAM = 0.52 ( 0.05. In another work on the 60DESA 2B 60 40 2
DMAEMASA monomer, Shirshin et al.14 investigated the 60DESA 5SUC 60 40 5 1
effects of initial concentrations of monomers and initiators in
60DESA 10SUC 60 40 10 1
the copolymerization of DMAEMASA and acrylonitrile (AN).
60DESA 5PEG 60 40 5 1
The novel gels poly(N,N0 -dimethylaminoethyl methacrylate
sulfate) (PDMAEMASA) and P(DMAEMASA-co-DMAm) were 60DESA 10PEG 60 40 10 1
prepared in the absence and presence of pore-forming agents 60DESA 5NaHCO3 60 40 5 1
NaHCO3, poly(ethylene glycol) 2000, and sucrose, and they 60DESA 10NaHCO3 60 40 10 1
were characterized. A comparison between the properties 80DESA 80 20 1
of porous and nonporous DMAEMASA homopolymer and 80DESA 2B 80 20 2
DMAEMASA-DMAm copolymers was also performed for the 80DESA 5SUC 80 20 5 1
first time in this work. 80DESA 10SUC 80 20 10 1
80DESA 5PEG 80 20 5 1
2. EXPERIMENTAL SECTION 80DESA 10PEG 80 20 10 1
80DESA 5NaHCO3 80 20 5 1
2.1. Materials. DMAm monomer and the cross-linker
80DESA 10NaHCO3 80 20 10 1
N,N0 -methylene bisacrylamide (NMBA) were purchased from
100DESA 100 1
Fluka (Sigma-Aldrich) and Merck (Hohenbrunn, Germany),
respectively. DMAEMASA was prepared from DMAEMA 100DESA 2B 100 2
(Merck, Hohenbrunn-Germany) and sulphuric acid (Merck, 100DESA 5SUC 100 5 1
Hohenbrunn-Germany). The initiator ammonium persulfate 100DESA 10SUC 100 10 1
(APS) and the accelerator N,N,N0 ,N0 -tetramethylethylenedia- 100DESA 5PEG 100 5 1
mine (TEMED) were purchased from Riedel-de H€aen (Seelze, 100DESA 10PEG 100 10 1
Germany) and Serva Electrophoresis GmbH (Heidelberg, 100DESA 5NaHCO3 100 5 1
Germany), respectively. Pore-forming agents NaHCO3, sucrose 100DESA 10NaHCO3 100 10 1
(SUC), and poly(ethylene glycol) 2000 (PEG) were Riedel-de a
Pore-forming agents were used in 5 and 10 wt % of total monomer
H€aen (Seelze, Germany), Carlo Erba (Milan, Italy), and Merck amounts. b NMBA was used in mol percentages of total monomer
(Hohenbrunn, Germany) products, respectively. Buffer solu- content. Initiator APS was used in 1 mol percentages of total monomer
tions were prepared15 by using potassium hydrogen phthalate, content. Accelerator TEMED was used in the equal amount of APS
potassium dihydrogen phosphate, HCl (37% aqueous solution), in gram.
sodium bicarbonate, sodium chloride, and sodium hydroxide.
Buffer chemicals were Merck (Hohenbrunn, Germany) pro- hydrogels are presented in Table 1. In polymer codes, DMAE-
ducts, except sodium bicarbonate and sodium chloride, which MASA is represented by DESA. The numerals before DESA in
were obtained from Riedel-de H€aen, and sodium hydroxide, polymer codes show the mol percentage of DMAEMASA mono-
which was produced by JT Baker. Distilled water was used for the mer in monomer mixture, and the rest is DMAm content. The
preparation of hydrogels and buffer solutions, and for swelling numerals, i.e., 5 or 10 before the pore-formers SUC, PEG, and
measurements. NaHCO3 show the amounts of pore-forming agents in weight
2.2. Synthesis of DMAEMASA Monomer13. An appropriate percentage of total monomer amount. For example, 100 DESA
amount of DMAEMA monomer was placed in a glass tube that and 100 DESA 2B show the homopolymers of DMAEMASA
was immersed in an ice bath in order to keep the temperature prepared in the presence of 1 and 2 mol % of NMBA (B) as cross-
of the reaction mixture below 15 °C, as the reaction of DMAE- linker, respectively.
MA with H2SO4 is exothermic.13 A stoichiometric amount Polymerization reactions were performed in glass tubes with
of H2SO4 (98%) was then added to DMAEMA monomer drop an inner diameter of 1.3 cm and a length of 15 cm. An aqueous
by drop with magnetic stirring. The quaternary sulfate salt solution of ammonium persulfate (APS) (4.25 g APS/100 mL
(DMAEMASA) of DMAEMA monomer was a white solid that water) and N,N,N0 ,N0 -tetramethylethylenediamine (TEMED)
was used without further treatment. Please see our previous were used as initiator and accelerator, respectively. Hydrogels
paper16 for further information about DMAEMASA monomer. with different feed compositions were prepared by varying the
2.3. Synthesis of Hydrogels. A series of cationic copolymer DMAm content of the monomer mixture from 20 and 40 mol %
gels of N,N0 -dimethylaminoethyl methacrylate sulfate (DMAEM- at a constant total initial monomer concentration of 1 M, while
ASA) with N,N-dimethyl acrylamide (DMAm) P(DMAEMASA- the cross-linking agent was kept constant at 1 mol % of the total
co-DMAm) and DMAEMASA homopolymer were prepared monomer content for porous gels, but 1 and 2 mol % for
in aqueous solution at 40 °C for 24 h in the presence or absence nonporous gels. Before the polymerization, the monomer solu-
of pore-forming agents; NaHCO3, sucrose (SUC), and poly- tion containing cross-linker and pore-forming agent (PEG or
(ethylene glycol) 2000 (PEG) using N,N0 -methylene bis acryla- SUC) was bubbled with nitrogen gas for 15 min, followed by the
mide (NMBA) as the cross-linker. The feed compositions of the addition of the initiator and accelerator. Porogen NaHCO3 was
8296 dx.doi.org/10.1021/ie102349p |Ind. Eng. Chem. Res. 2011, 50, 8295–8303
Industrial & Engineering Chemistry Research
Figure 1. (a) Optical appearances of DMAEMASA-DMAm hydrogels
in glass tubes just after preparation. (b) Optical appearances of swollen
DMAEMASA and DMAEMASA- DMAm gels in distilled water.
added to the reaction mixture after the addition of the initiator
and accelerator in order to prevent the earlier decomposition of
porogen. The tubes were then sealed and immersed for 24 h in a
water bath at 40 °C ((0.01 °C). At the end of the reaction
period, the tubes were broken carefully without destroying the
hydrogels. The cylindrical hydrogel was then sliced into small
discs (0.6
0.8 cm in length), which were stored in distilled water
for one week. The water was changed twice daily to remove the
sol fraction (the residual unreacted monomers and linear poly-
mers). The resulting swollen hydrogel discs were dried, first in air
and then in a vacuum oven at 40 °C.
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Figure 2. FTIR spectra of nonporous (a) and porous (b) DMAEMASA
homopolymer and copolymer gels.
2.4. Optical Appearances of Hydrogels. The optical pic-
tures of the hydrogels were recorded by a digital camera
(Canon, A610) in order to observe the effects of porogens
on the microheterogeneity, and thus on the transparency of
the hydrogels. The pictures of the hydrogels are given in
Figure 1a and b.
2.5. FTIR Measurements. FTIR spectra of the dry gels were
recorded using an ATR technique (Perkin-Elmer Spectrum
One). FTIR spectra of DMAEMASA homopolymer and DMAE-
MASA-DMAm gels are presented in Figure 2a and b.
2.6. Surface Morphology of the Polymers. The morphol-
ogies of DMAEMASA homopolymer and P(DMAEMASA-co-
DMAm) gels were investigated using a scanning electron micro-
scope (JEOL, JSM 5600). Before investigation, the hydrogels
were dried at
45 °C and 38.10
3 mmHg using a vacuum freeze-
dryer (Armfield SB4), following which their surfaces were
sputter-coated with gold. A few representative SEM micrographs
are given in Figure 3 for the investigation of the interior matrix
structure of DMAEMASA homopolymer and P(DMAEMASA-
co-DMAm) gels synthesized in the absence or presence of pore-
forming agents.
2.7. Effect of Temperature on the Equilibrium Swelling
Values. The ESVs of DMAEMASA homopolymer and DMAE-
MASA-DAAm copolymer gels were determined at 20, 30, 40, and
60 °C in distilled water by the gravimetric method. A given
amount of dry gel (Wd) was immersed in distilled water at the
desired temperature for 24 h in order to attain the swelling
equilibrium. At the end of the swelling period, swollen gel pieces
were taken out of water, blotted with a piece of filter paper to
remove excess water, and weighed (Ws). ESVs of the gels were
dx.doi.org/10.1021/ie102349p |Ind. Eng. Chem. Res. 2011, 50, 8295–8303
Industrial & Engineering Chemistry Research
Figure 3. SEM micrographs of porous and nonporous DMAEMASA and DMAEMASA-DMAM gels.
determined by the following equation:
Equilibrium Swelling Value ðESVÞ ðg H2 O=g polymerÞ
¼ ðW s
W d Þ=W d ð1Þ
2.8. Effect of pH of the Swelling Medium on the Equilib-
rium Swelling Values. A given amount of dry gel (Wd) was
immersed in buffer solutions with different pH values and
constant ionic strength (I = 0.1 M) at 20 °C for 24 h in order
to investigate the effects of pH and pore-forming agents on the
ESVs of the gels. Different formulations of the buffer solutions15
in a wide range of pH values were prepared, e.g., potassium
hydrogen phthalate
HCl at pH 2.2 and 2.8, potassium hydrogen
phthalate
NaOH at pH 5.0, potassium dihydrogen phosphate

NaOH at pH 7.0, diethanolamine
HCl at pH 8.5, and sodium
bicarbonate
NaOH at pH 10.0. After the preparation of buffer
solutions, their pH values were checked by a pH meter (Thermo
Scientific ORION 3 STAR), and no unsuitability was detected
between the experimental and theoretical pH values of buffer
solutions. The ionic strength of each buffer solution was kept
constant at 0.1 M by the addition of NaCl as necessary. ESVs of
gels in buffer solutions were determined using eq 1.
2.9. Elemental Analysis of Copolymers. Elemental analysis
of dry DMAEMASA homopolymer and DMAEMASA-DMAm
copolymer gels was performed using a Flash EA 1112 model of a
Thermo Finnigan instrument. DMAEMASA content of DMAE-
MASA-DMAm gels in weight percentage was calculated17 by
S (sulfur) contents of DMAEMASA monomer and copolymer
gels using eq 2.
DMAEMASA ðwt %Þ ¼ ðS=So Þ  100 ð2Þ
where S and So are the sulfur contents (in wt %) of copolymer
and DMEMASA monomer, respectively, determined by elemen-
tal analysis.
2.10. Differential Scanning Calorimetry (DSC) Measure-
ments. Glass transition temperatures (Tg) of porous or
nonporous DMAEMASA and DMAEMASA-DMAm gels were
determined using 15
20 mg polymer by a SETARAM 131
instrument under a nitrogen atmosphere with a heating rate
of 10 °C/min.
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ARTICLE
3. RESULTS AND DISCUSSION
3.1. Synthesis and Characterization of Novel Porous/
Nonporous DMAEMASA and P(DMAEMASA-co-DMAm)
Gels. A few representative photographs of DMAEMASA homo-
polymer and P(DMAEMASA-co-DMAm) gels are shown in
Figure 1a and b. They show the hydrogels in glass tubes just
after preparation, and CO2 bubbles are also seen in the pictures of
hydrogels prepared in the presence of NaHCO3. The swollen
homopolymer and copolymer slices that were purified by the
removal of sol fraction are seen Figure 1b. Both porous and
nonporous hydrogels for all monomer compositions are highly
elastic and transparent in appearance, implying the absence of
impurities such as porogens and microheterogeneity in the
polymer structure. Ozmen et al.18 have reported that if the
amount of water in the polymerization mixture is higher than
the swelling capacity of the gel, it cannot absorb all the water in
the polymerization medium, thus a phase separation occurs
during the polymer formation. Finally, an opaque gel is obtained.
They also concluded that if the volume of swollen gel is higher
than the volume of the just prepared-gel, no phase-separation is
observed. Otherwise, the system will be two-phased, and opaque
in appearance. It was also reported that the ionization of polymer
hydrogels suppresses the inhomogeneities.19 Because DMAE-
MASA homopolymer and its copolymer with DMAM are ionic in
nature, the transparency of these porous gels may be attributed to
suppression of inhomogeneities.
FTIR spectrum of DMAEMASA monomer was given in our
previous paper.16 Characteristic bands in FTIR spectrum
of DMAEMASA were seen at 3048 cm
1 (the stretching vibra-
tion of C
H in CdC double bond of CH2dC(CH3)— group),
at about 2500 cm
1 (the NR3Hþ group which is characteristic
for protonated DMAEMASA monomer20), at 1719 cm
1
(νCdO),21 at 1470 cm
1 (asymmetric in-plane bending of
C
H bond in
CH2 and
CH3 groups of monomer and
C
N stretching,21
23 and at 1030 cm
1 (strong) and 1228 cm
1
(weak) (symmetric and asymmetric
SO2 stretchings,24,25 re-
spectively). Asymmetric and symmetric C
O
C stretchings21
were represented by two bands at 1145 cm
1 (strong) and
1298 cm
1 (weak), respectively.16
dx.doi.org/10.1021/ie102349p |Ind. Eng. Chem. Res. 2011, 50, 8295–8303
Industrial & Engineering Chemistry Research ARTICLE

FTIR spectra of DMAEMASA homopolymer (100 DESA) Table 2. Glass Transition Temperatures (Tg) and Results for
and its copolymers with 20 and 40 mol % DMAm (80 DESA and Elemental Analysis of Porous and Nonporous DMAEMASA
60 DESA) are given in Figure 2a. Homopolymer and DMAEMASA-DMAm Copolymer Gels
FTIR spectrum of nonporous homopolymer (100 DESA)
sulfur content DMAEMASA
contains all the characteristic bands of DMAEMASA monomer
except that for CdC double bond. The appearance of a new band polymer code (S) (wt %) content (wt %) Tg (oC)
at 1627 cm
1 (amide I: νCdO) in the spectrum of 80 DESA 60DESA 6.7 64.1 147.8
confirms the presence of DMAm in copolymer structure. The 60DESA 5SUC 5.7 54.5 148.5
intensity of that band increased with DMAm content as can 60DESA 10SUC 5.2 49.8 140.8
be seen in the spectrum of 60 DESA (1623 cm
1) (Figure 2a).
60DESA 5PEG 5.1 48.8 149.0
One of the changes that occurs due to DMAm incorporation in
60DESA 10PEG 5.7 54.5 147.2
the polymer structure is the decrease in the intensity of the band
due to NR3Hþ structure. The shift in amide I band (νCdO) 60DESA 5NaHCO3 5.0 47.9 148.2
from 1627 cm
1 (80 DESA) to 1623 cm
1 (60 DESA) confirms 60DESA 10NaHCO3 4.9 46.9 145.7
the presence of hydrogen bondings between carbonyl group of 80DESA 8.5 81.3 154.6
DMAm and
OH and
NH groups of DMAEMASA. It is 80DESA 5SUC 7.3 69.8 146.8
known that there are hydrogen bondings between the polymers 80DESA 10SUC 7.4 70.8 148.5
containing hydroxyl groups and tertiary amide polymers. This 80DESA 5PEG 7.1 67.9 153.3
kind of interaction is confirmed by the shift of carbonyl band in 80DESA 10PEG 6.7 64.1 156.6
FTIR spectrum to lower frequencies.26 The intensity of the band 80DESA 5NaHCO3 6.5 62.2 156.5
at 1143 cm
1 increased with the incorporation and content 80DESA 10NaHCO3 6.5 62.2 155.7
of DMAm.
100DESA 8.4 80.4 168.4
There is no difference between the FTIR spectra of porous
100DESA 5SUC 8.8 84.2 156.3
and nonporous DMAEMASA-DMAm copolymers (Figure 2b).
This finding confirms that the pore-forming agents (NaHCO3, 100DESA 10SUC 8.8 84.2 158.5
sucrose, and poly(ethylene glycol) 2000) are extracted by water 100DESA 5PEG 10.1 96.7 160.2
from the copolymer during the removal of sol fraction in the 100DESA 10PEG 8.4 80.4 167.3
purification step, and they have no interaction with the polymer. 00DESA 5NaHCO3 7.6 72.7 161.8
The structural morphology of porous and nonporous DMAE- 100DESA 10NaHCO3 7.3 69.9 165.1
MASA and (DMAEMASA-co-DMAm) gels was investigated by
SEM, and some representative SEM micrographs are given in The pore-formers PEG and SUC have nearly no effect on
Figure 3. Both DMAEMASA homopolymer and DMAEMASA- DMAEMASA content of homopolymer, but they decreased
DMAm copolymers prepared in the presence of pore-forming DMAEMASA content of 80 DESA and 60 DESA copolymers
agents have apparently more porous structure than the polymers at the same amount.
synthesized in the absence of porogens. 3.2. Differential Scanning Analysis (DSC) of DMAEMASA
Sulfur and DMAEMASA contents of porous and nonporous Homopolymer and DMAEMASA-DMAm Copolymers. Glass
DMAEMASA homopolymer and DMAEMASA-DMAm copo- transition temperatures (Tg) of porous and nonporous DMAE-
lymers are given in Table 2. Sulfur content of DMAEMASA MASA homopolymer and DMAEMASA-DMAm copolymers
monomer (So) was found to be 10.45 wt %, and it is 83% are given in Figure 5 and Table 2. Tg values of DMAm homo-
of theoretical amount. When the contents of C, H, and N of polymer are given as 11826 and 122.4 °C.27 Bae et al.28 synthe-
DMAEMASA monomer are evaluated together with S contents, sized copolymers from DMAm and 2-(N-ethyl-perfluorooctane-
it can be concluded that DMAEMASA contains a small amount sulfonamido) acrylamide (FOSA) with up to 5 mol % FOSA, and
of DMAEMA that is not converted to quaternary sulfate salt. reported that the Tg values of these copolymers were 110

Analysis results for C, H, and N contents of polymers are 3
13% 120 °C. Whereas Tg values of DMAEMA homopolymer are
higher than those of theoretical values (not provided). This given as 20,29 14,30 1931,32 and 12 °C,33 no DSC analysis either
difference can be assigned to the presence of water which could for DMAEMASA homopolymer or DMAEMASA-DMAm co-
not be removed from the gel during drying. In contrast to the polymer has been reported in literature until now since they are
results for C, H, and N contents, experimental DMAEMASA novel polymers.
contents of the polymers are approximately 70% of theoretical Tg values of DMAEMASA homopolymer (100 DESA) and the
DMAEMASA values. This result indicates that DMAEMASA- copolymers 80 DESA and 60 DESA were found to be 168.4,
DMAm gel contains DMAEMA units too, and that the former is a 154.6, and 147.8 °C, respectively (Figure 5). This finding
terpolymer. The effect of the use of pore-forming agents on the S indicates that the introduction of DMAm in polymer structure
namely DMAEMASA contents of polymers is given Figure 4 and and further increase in its content lead to decrease in Tg of
Table 2. The use of pore-forming agent during the polymer polymer. As can be understood from the molecular formulas of
synthesis decreases DMAEMASA content of polymer. This monomers used in the polymer preparation, DMAEMASA
decrease in DMAEMASA content is apparent especially for homopolymer has hydrogen atoms which are capable of making
porous 60 DESA and 80 DESA copolymers. Among the poro- hydrogen bondings, but it is not the case for DMAm homo-
gens NaHCO3, sucrose, and poly(ethylene glycol) 2000, the polymer. Therefore, Tg of the former polymer (168.4 °C) is
highest decrease in DMAEMASA content of polymer was higher than that of the latter given as about 120 °C in
created by NaHCO3. This higher effect of NaHCO3 on DMAE- literature.26,27 Therefore, the copolymerization of DMAEMASA
MASA content of polymer can be attributed to the neutralization with DMAm reduced the Tg of copolymer. In general, the
of some part of acidic DMAEMASA monomer with NaHCO3. presence of pore-forming agents such as NaHCO3 and PEG in
8299 dx.doi.org/10.1021/ie102349p |Ind. Eng. Chem. Res. 2011, 50, 8295–8303
Industrial & Engineering Chemistry Research
Figure 4. DMAEMASA contents (in wt %) of porous and nonporous
DMAEMASA homopolymer and DMAEMASA-DMAm copolymer gels.
Figure 5. Glass transition temperatures (Tg) of porous and nonporous
DMAEMASA homopolymer and DMAEMASA-DMAm copolymers.
polymerization medium had nearly no effect on the Tgs of porous
80 DESA and 60 DESA copolymers, but sucrose decreased the
Tgs of both homopolymer and copolymers. Highest decreasing
effect of sucrose on Tg of polymers was observed for those of
homopolymer (100 DESA polymer), and approximately 11 °C
decrease in Tg of homopolymer was determined due to use of
sucrose as pore-former. The decreases in Tgs of copolymers
80 DESA and 60 DESA due to the pore-former sucrose were
about 7 and 3 °C, respectively. Among the pore-formers, this
higher effect of sucrose in Tgs of polymers can be explained by the
difficulty in its removal during the purification of polymers.
3.3. Equilibrium Swelling Values of DMAEMASA Homo-
polymer and P(DMAEMASA-co-DMAm) Gels Depending on
Temperature of the Swelling Medium. The variation of
equilibrium swelling values (ESVs) of DMAEMASA homo-
polymer (100 DESA) and DMAEMASA-DMAm copolymers
with temperature depending on cross-linker content is given in
Figure 6. The increase in cross-linker (NMBA) content in
monomer mixture from 1 to 2 mol % decreased the ESVs
of both homopolymer and copolymers. In addition, the
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ARTICLE
Figure 6. Equilibrium swelling values of nonporous DMAEMASA and
DMAEMASA-DMAm gels with two different cross-linker contents in
distilled water as a function of temperature.
introduction of DMAm in polymer structure and further increase
in its content in monomer mixture increased the ESVs of
polymers. As noted before, intermolecular hydrogen bondings
in 100 DESA polymer decrease the swelling capacity of polymer.
In nonporous copolymer (80 DESA and 60 DESA) structure, the
presence of DMAm decreases the concentration of hydrogen
atoms which are capable of making intra- or intermolecular
hydrogen bondings because it has no hydrogen atom bound to
nitrogen or oxygen atom. Thus, the higher ESVs of copolymers
can be explained by the decrease in hydrogen bondings between
polymer chains. Bae et al.28 have also observed that the incor-
poration of DMAm is more efficient on the water absorption
values of NIPAM terpolymers (NIPAM/AAm/FOSA and NI-
PAM/DMAm/FOSA) than that of acrylamide (AAm). This
finding is consistent with our finding. The effects of pore-forming
agents on the ESVs of DMAEMASA homopolymer and DMAE-
MASA-DMAm copolymers in distilled water at various tempera-
tures are given in Figure 7 a
c. The swelling capacity of 100
DESA slightly increased with the increase in temperature from 20
to 60 °C as can be expected (Figure 7a). The use of pore-forming
agents such as NaHCO3, sucrose, and PEG enhanced the water
absorption capacity of homopolymer. Furthermore, higher im-
provements in ESVs of homopolymer were determined with the
increase in the content of pore-former from 5 to 10%. Among the
pore-forming agents used in this work, the highest enhancement
on the ESV of homopolymer was performed by NaHCO3.
Similar findings on the ESV’s of copolymers are seen in Figures 7
b and c. Twice increase in PEG and sucrose amounts had nearly
the same and comparatively low amount of improvement on the
swelling of both homopolymer and copolymers in distilled water.
When NaHCO3 amount in polymerization medium doubled, an
apparently higher amount of improvement in the swelling of
porous gels was observed in comparison to the effects of PEG
and sucrose.
3.4. Equilibrium Swelling Values of DMAEMASA Homo-
polymer and DMAEMASA-DMAm Gels Depending on pH of
the Swelling Medium. The variation of ESVs of porous and
nonporous DMAEMASA homopolymer (100 DESA) and co-
polymers (80 DESA and 60 DESA) with pH of swelling medium
are given in Figure 8a
c. While nonporous DMAEMASA homo-
polymer has lowest ESVs in buffer solutions at pH range of
2
10, homopolymer synthesized with 10% NaHCO3 (100
DESA 10 NaHCO3) displayed highest amount of swelling in
dx.doi.org/10.1021/ie102349p |Ind. Eng. Chem. Res. 2011, 50, 8295–8303
Industrial & Engineering Chemistry Research
Figure 7. Equilibrium swelling values of DMAEMASA and DMAE-
MASA-DMAm gels in distilled water as a function of temperature.
buffer solutions at all pH values (Figure 8a). The increase in
pore-formers’ content led to an apparent improvement in ESV of
100 DESA. ESV of homopolymer in acidic medium at pH = 2 is
higher than those at neutral and basic pHs, and it decreases with
the increase in pH up to 5. The decrease in ESV of DMAEMASA
homopolymer with the increase in pH from 2 to 5 can be
explained by the decrease and dissappearance in protonation of
polymer. In general, cross-linked cationic polymers have higher
water absorption capacities at low pHs due to repulsion forces
between the positive-charged polymer chains. They display
lower swelling at neutral and alkaline pHs, because the polymer
is in noncharged structure at these pHs. The increase in ESV
of homopolymer with pH after pH = 5 may be attributed to
the partial neutralization of DMAEMASA unit (or pendant
group of DMAEMASA) of polymer to DMAEMA with NaOH
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ARTICLE
Figure 8. Equilibrium swelling values of DMAEMASA and DMAE-
MASA-DMAm gels in buffer solutions (20 °C) as a function of pH of
swelling medium.
in buffer solutions with pH = 7 and 10 during the swelling.
As seen, ESVs of copolymers decrease with the increase in
DMAEMASA content and the homopolymer has lowest water
absorption capacity due to inter- or intramolecular hydrogen
bondings between polymer chains. The interaction of DMAE-
MASA unit of polymer with a constituent of buffer solution
during swelling is confirmed by the decrease in the increases in
swelling of polymer with the decrease in DMAEMASA content
(60 DESA copolymer) of polymer at pH range of 5
10. The
same swelling and pH relationship are valid for 80 DESA and 60
dx.doi.org/10.1021/ie102349p |Ind. Eng. Chem. Res. 2011, 50, 8295–8303
Industrial & Engineering Chemistry Research
DESA copolymers in buffer solutions at pH range of 2 and 10.
The decrease in ESV of polymer with DMAEMASA content was
also observed for DMAEMASA-NIPAM copolymers.16 Zhang
et al.10 reported that the swelling of porous NIPAM gels
increased with the increase of pore-formers (sucrose) content,
consistent with our findings. In the swelling of both homopoly-
mer and copolymer gels with pH range of 2
10 (Figure 8a
c),
the increase in NaHCO3 and sucrose content from 5 to 10 wt %
showed nearly the same amount of effect on the swelling
values, but doubling the PEG content slightly affected the
swelling of the copolymers such as 80 DESA 5 PEG and
60 DESA 5 PEG. As to the effect of NaHCO3 on the swelling
of both homopolymer and copolymers, the lowest increase
in ESV due to NaHCO3 was observed for those of homo-
polymer. During the synthesis of porous polymer with the use
of NaHCO3 as porogen, gelation rate, and the concentrations
of initiator, monomer, and cross-linker are important parameters
affecting the porosity of polymer gel as well as the amount of
porogen. If the gelation occurs in a longer time (slow gelation),
and the evolution of CO2 through decomposition of NaHCO3
takes place fast, porous gel can not be obtained. Bune et al.13
reported that the polymerization rate of DMAEMASA with
acrylamide (AAm) decreases with DMAEMASA content in
monomer feed up to 40 mol %. The lower contribution to the
swelling of homopolymer with twice increase in NaHCO3
content in comparison to the effect on those of copolymers
may be explained by the following reasons:
1. The rate of gelation in the formation of DMAEMASA
homopolymer will be slower than that of copolymerization
of DMAEMASA and DMAm due to repulsion forces of
positive-charged pendant group of DMAEMASA.
2. In homopolymer structure, the formation of inter- or
intramolecular hydrogen bondings is more favored in com-
parison to the copolymer. These hydrogen bondings play a
role as additional cross-links, and they decrease the ESV of
polymer.
4. CONCLUSIONS
Novel DMAEMASA homopolymer and DMAEMASA-DMAm
copolymers were synthesized in the presence and absence of
pore-forming agents NaHCO3, sucrose, and poly(ethylene glycol)
2000. The effects of kinds and contents of pore-forming agents
on the swelling of polymers were determined by equilibrium
swelling measurements in distilled water and buffer solutions,
FTIR, elemental analysis, DSC, and SEM methods. The elemental
analysis results showed that DMAEMASA homopolymer and its
copolymer with DMAm are a copolymer and a terpolymer, respec-
tively, containing DMAEMA as well. The presence of DMAEMA in
homopolymer and copolymer may be attributed to the high affinity
of DMAEMASA to water, and the partial neutralization of DMAE-
MASA by the accelerator TEMED and pore-former NaHCO3
during the polymerization.
DMAEMASA homopolymer has the lowest ESVs both in
distilled water and buffer solutions due to intermolecular hydro-
gen bondings. DMAm constituent of the copolymer decreased
the formation of intermolecular hydrogen bondings, and thus the
ESV of copolymer increased with DMAm content.
Both homopolymer and copolymers displayed highest
amount of water absorption at low pH due to repulsion forces
between the protonated polymer chains. ESVs of polymers
decreased with pH up to 5, and then they increased slightly with
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ARTICLE
further increase in pH, most probably due to the partial conver-
sion of DMAEMASA unit of polymer to DMAEMA by its
neutralization with NaOH in buffer solution.
Glass transition temperature of DMAEMASA homopolymer
gel was determined to be 168.4 °C. DMAm decreased the Tg of
copolymer due to the decrease in intermolecular hydrogen
bondings. Porogens decreased the Tg of homopolymer too in
the order of NaHCO3 < PEG < SUC, and among them, sucrose
led to 11 °C decrease in Tg of homopolymer. In case of copoly-
mers, NaHCO3 and PEG had no apparent effect on Tgs of
copolymers, but sucrose led to 7 °C decrease in glass transition
temperature of copolymer. NaHCO3 has highest effect on the
swelling of both DMAEMASA homopolymer and DMAEMA-
SA-DMAm copolymer gels in comparison to PEG and sucrose.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: ggurdag@istanbul.edu.tr. Phone: þ90 212 473 70 00.
Fax: þ90 212 473 71 80.
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