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Preparation and characterization of a new family of bio-interpenetrating

network hydrogel based on a green method

Article in Egyptian Journal of Chemistry · August 2021

DOI: 10.21608/ejchem.2021.78987.3991

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 720 Egypt. J. Chem. Vol. 64, No. 12 pp. 7451 - 7464 (2021)

Egyptian Journal of Chemistry

http://ejchem.journals.ekb.eg/

Preparation and Characterization of A New Family Of Bio-Interpenetrating Network

Hydrogel Based On A Green Method

Alaa I.E. Abdelaziza*, S.M .Elsaeeda, E.G. Zakia, M.M. Aboalyb, M.E.S. Abdel-Raoufa, A.M .Al-Sabagha
a
Egyptian Petroleum Research Institute, 1 Ahmed El-Zomer Street, Nasr City, 11727, Cairo, Egypt.
b
Chemistry Department, Faculty of Science, Ain Shams University, Cairo, Egypt.

Abstract

In this work, semi-interpenetrating polymer network hydrogels with and without castor oil (S-2IPNC, S-3IPNC, S-4IPNC,
S-2IPN, S-3IPN and S-4IPN) are synthesized using a free-radical solution polymerization in presence of acrylic acid as a pH-
responsive monomer and dimethyl aminoethyl methacrylate as a thermoresponsive monomer with carboxymethyl cellulose
(CMC) as a cellulose derivative, potassium persulphate and N, N'-methylene bisacrylamide. Castor oil, as a green chemical
material, is incorporated with a ratio (1:2) to CMC. The semi-interpenetrating network structures are formed and justifications
are done by ATR-FTIR and Raman spectroscopy to assure their chemical composition. TGA, SEM, XRD and AFM approve
thermogravimetric analysis, phase morphology, crystallinity and surface topography, respectively. The results show that the
addition of castor oil enhances the texture and stability of hydrogels. It is concluded that S-IPNC hydrogels show higher
swelling capacity than S-IPN hydrogels at lower NaCl concentration and pH range (5-7), due to increasing the osmotic
pressure.Therefore, castor oil could be used as a green material in interpenetrating network hydrogels for water-saving
applications.According to the principle of sustainable growth, environmentally biopolymer hydrogels pose a significant
potential for using as water storage in the agricultural sector.

Keywords: AFM; Castor oil; Dimethyl aminoethyl; Interpenetrating polymer network (IPN); Swelling behavior; Thermal analysis.

1. Introduction [12, 13], printing applications[14], drug delivery[15,

The principles of green chemistry are widely 16], tissue engineering[17, 18], sensor and actuator
spreading through industrial processes. The main [19-21] and solar cells [22-26].
reason for using green chemistry is to reduce IPNs (interpenetrated polymer networks) are three-
problems related to human health and environmental dimensional polymer networks that combine two
risks by replacement of petroleum-based materials polymers at least one of them is cross-linked or
with natural polymer materials involved in different synthesized in the network form using various
applications[1-3].The hydrogel is known as a functional groups that have high water-swelling
network formed of crosslinked polymers that can properties.
hold the absorbed water within its pores due to the IPNs are better than hydrogels as they have different
presence of hydrophilic groups, such as carboxyl and characteristics that enhance the swelling capacity,
hydroxyl groups, in their polymer chains[4, 5]. A mechanical properties and are stable in a wide pH
distinct group is that of macromolecular hydrogels, range and at high temperatures [27].
composed of superabsorbent hydrogels that can Thermoresponsive hydrogels exhibit a phase
absorb huge quantities of water and retain it [6, 7]. separation and volume change above a definite
They show biodegradability, high swelling rate (SR), temperature.
excellent water retention ratio (WRR) and high There are two main types of thermoresponsive
swelling capacity [8, 9], which endows them to have polymers; the first is a lower critical solution
widespread practical applications such as hygienic temperature (LCST) and the second is upper critical
products[10],agriculture[11],wastewater treatment solution temperature (UCST). LCST and UCST are

_________________________________________________________________________________________________
* Corresponding author e-mail: [email protected]
Receive Date: 13 June 2021, Revise Date: 14 August 2021, Accept Date: 16 August 2021
DOI: 10.21608/EJCHEM.2021.78987.3991
©2021 National Information and Documentation Center (NIDOC)
7452 Alaa I. E. Abdelaziz et.al.
_____________________________________________________________________________________________________________

the critical temperature points where polymer and based polymers to be industrialized and used for
solvent become miscible below and above it upcoming applications [40].
respectively. These hydrogels shrink upon heating The aim of this work concentrates on three objects,
above LCST as they become insoluble and more the first one is to synthesize a new family of bio-
hydrophobic and that leads to gel formation and interpenetrating network hydrogels of DMAEMA
soluble below LCST. On the contrary, hydrogels monomer with acrylate monomer (AA) using a redox
have positive temperature-sensitive shrink upon initiator as potassium persulfate (KPS) and a
cooling below the UCST and swell above it [28]. crosslinking agent as N, N′-methylene bisacrylamide
Poly(N-isopropylacrylamide) (PNIPAM) and (MBA), based on green chemicals such as
poly(dimethyl aminoethyl methacrylate) carboxymethyl cellulose (CMC) and castor oil. The
(PDMAEMA) resemble the most important second object is confirmation their chemical
temperature-responsive polymers, as the LCST of structures using ATR-FTIR, Raman spectroscopy,
PNIPAM is 32 oC [29] while that for PDMAEMA is TGA, SEM, XRD and AFM. The third objective is
around 14-50 oC [30]. the incorporation of castor oil in IPNs and
Carboxymethylcellulose (CMC) is a cellulose investigating their swelling properties under different
derivative and considers as an essential polymer in conditions, studying their re-ability for swelling-
different industrial applications. CMC, among all the deswelling, so we could predict their use in
polysaccharides, is very cheap and easily abundant environmental/agriculture applications.
[31]. Vegetable oils are bio-renewable resources
extracted from different plants such as palm oil,
soybean oil and castor oil. 2. Materials and methods
Castor oil is a renewable and cost-competitive 2.1. Materials
environmental resource, it also has good flexibility
and elasticity due to the presence of a long fatty acid Acrylic acid (AA, analytical grade, Fluka, Germany).
chain, and it leads itself as a thermosetting type dimethyl aminoethyl methacrylate (DMAEMA,
material due to its trifunctional nature. It also has a analytical grade, Sigma-Aldrich).
unique structure, with about 90% of the fatty acid Carboxymethylcellulose (CMC, National Company).
chains being ricinoleic acid, which bears a hydroxyl N,N′-methylene bisacrylamide (MBA, ACROS
group, making it a useful vegetable oil in the
organic). sodium chloride (NaCl) and potassium
industrial field. As a result of the hydroxyl groups
persulphate (KPS) were purchased from ADWICK
and carbon-carbon double bonds, it is useful in a
variety of chemical processes[32, 33]. Moreover, ”commercial”. sodium hydroxide (NaOH , Fisher
castor oil, among all vegetable oils, is considered as Chemical Scientific Lab). Castor oil was purchased
one of the most plentifully and naturally occurring from the local market and found to contain hydroxyl
oils, which can be used for the improvement of the value 160-162 mg KOH/g, corresponding to 2.7
polymers with tremendous properties that can be used hydroxyl groups per mole of castor oil. All reagents
for numerous applications like lubricants, coating, were used without further purification. Deionized
etc. [34]. Polyols based on vegetable oils, as widely water was used throughout the work.
plentiful raw materials, have found many essential
applications [11]. For example, polyols based on 2.2. Preparation of CMC/Poly(AA-DMAEMA)
castor oil are considered environment-friendly and semi-interpenetrating polymer network with
reasonable in cost [35, 36]. Adding castor oil to CMC castor oil (S-IPNC) and without castor oil (S-
aims to provide a novel technique to enhance the IPN)
interfacial adhesion and improve polymer network
connectivity This work introduces preparation of a new
IPNs prepared using castor oil showed enhanced simultaneous interpenetrating polymer network
mechanical properties, electrical properties and where acrylate monomer AA and DMAEMA
thermal stability due to high crosslinking density and monomer were in situ polymerize, in presence of
high content of hydroxyl in castor oil in comparison CMC and castor oil, along with initiator, one is
with other vegetable oils [37, 38]. So, IPNs from crosslinked by MBA to form a polymer network
castor oil have been developed for different industrial while the other monomer forms a linear polymer
applications [39]. In contrast with different vegetable which entrapped into the matrix to form finally a
oils, castor oil can be stored for a long time and stay semi IPN.
usable. Castor oil, as a renewable source, can be The desired amount of reactants were placed in a 250
utilized as a starting material in the synthesis of bio- ml flask (four-necked) with a condenser, magnetic
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stirrer and a thermometer equipped with a nitrogen of work and the voltage of excitation was 20 kV with
line. The superabsorbent hydrogels were synthesized an in-lens detector.
using a free-radical polymerization [41]. In the case (b) Atomic force microscope
of IPNC, CMC and castor oil (2:1) were dispersed The surface morphology of prepared hydrogel was
into 100 ml of distilled water by constantly stirring investigated using an atomic force microscope (AFM,
for 2 hrs at 60 o C. About 0.074 g of KPS was added Flexaxiom Nanosurf, Switzerland).0.1g of the sample
into this dispersion and the mixture was stirred for 10 was crushed into a fine powder then placed onto a
min at 60 oC to generate radicals, after that, desired sample holder. The samples were scanned by contact
ratios of DMAEMA were added in accordance with mode. The image size was 10 µm with a constant
neutralized Acrylic acid (AA) to the CMC solution force 20 nN in air environment with a temperature
then cooling to 40 oC and finally 0.074 gm of MBA 20–25 oC.
was added to terminate the reaction. X-ray diffraction
To complete the polymerization reaction, the X-ray diffraction (XRD) patterns of samples was
temperature was rose gradually to be at 70 oC and recorded using a PANalytical diffractometer
kept for 3hrs. (Siemens, AXSD5005) available at Egyptian
Then, the samples were immersed in distilled water petroleum research institute (EPRI) with Cu-Ka
to remove any unreacted components. Then the radiation (k = 1.54 Å) generated at 40 kV and 40mA
samples were put in the oven at 50-60 oC till constant in the differential angle (2θ) range of 4-80.
weight.
Conversely, in the case of IPN, castor oil was
removed and the same pre-mentioned steps were 2.4. Measurements of water absorption and
repeated. The codes and constitutions of the prepared swelling properties
hydrogels are given in Table 1(supplementary file).
The teabag method was used to perform swelling
2.3. Characterization techniques experiments. In this regard, an accurate weight of the
powdered hydrogel (0.05 ± 0.01 g) was put in a tea
Attenuated total reflection-Fourier transform bag and immersed into distilled water at room
infrared spectroscopy temperature (25 oC) for 4hrs. Then, the teabag was
The chemical structures were confirmed using an removed and excess water was allowed to drain. The
attenuated total reflection-Fourier transform infrared teabag was removed and allowed to remove excess
spectrophotometer (ATR-FTIR, Bruker Optik Gmbh water. Each sample was repeated at least 3 times,
Ettlingen, Germany), in the range of 4000–400 cm-1, with a maximum error bar ±0.5.
LUMO fully motorized stand-alone FTIR microscope The relation between swollen hydrogel weights and
in ATR mode. time was recorded every 30 min. Qmax (g g-1)
Raman spectroscopy represents water absorption of the hydrogels, it was
The Raman spectra were recorded with (Dispersive measured from the change in weight before and after
Raman Microscope, Bruker, Senterra) in the spectral absorption using the following equation (2.1) [7]:
range from 45-4500 cm-1. Excitation was done with a 𝐰𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐬𝐚𝐦𝐩𝐥𝐞 𝐚𝐟𝐭𝐞𝐫 𝐚𝐛𝐬𝐨𝐫𝐩𝐭𝐢𝐨𝐧
𝑸𝒎𝒂𝒙 = (2.1)
785 nm laser source. 𝒘𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐬𝐚𝐦𝐩𝐥𝐞 𝐛𝐞𝐟𝐨𝐫𝐞 𝐚𝐛𝐬𝐨𝐫𝐩𝐭𝐢𝐨𝐧
The absorbance of swollen water for the prepared
Thermogravimetric analysis hydrogels was verified under various conditions as
The decomposition profile of samples was follows.
thermogravimetrically analyzed using TGA 55
(Meslo, USA). Film samples were placed in a pan of
2.4.1. Swelling of prepared hydrogels at
platinum and heated in the range of 30 oC - 600 oC different temperatures
under N2 atmosphere at a heating rate of 10 oC per The swelling of prepared hydrogels was
minute and weight loss was plotted versus monitored at different temperatures (25 oC,
temperature. 35oC and 45 oC). The bags were removed from
Surface morphology techniques distilled water and then weighed. Then, Qmax
(a) Scanning electron microscopy with temperature was studied.
Scanning electron microscope (SEM) was used for
surface imaging using Quanta FEG 250 (FEI 2.4.2. Swelling of prepared hydrogels at
company, USA) available at Egyptian Desalination different salt concentrations
Research Center of Excellence (EDRC), Desert The swelling of hydrogel samples was done at
Research Center (DRC) in Egypt. Samples were different concentrations of NaCl saline solutions
mounted onto SEM stubs with 10.1 mm as a distance (0.2 M, 0.6 M and 1 M) at ambient temperature.
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Egypt. J. Chem. 64, No. 12 (2021)
7454 Alaa I. E. Abdelaziz et.al.
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Then Qmax was studied versus salt of the prepared polymer networks are shown in Fig.
concentration. (1).

2.4.3. Swelling of prepared hydrogels at

different pH
The prepared hydrogels were immersed in
distilled water with various pH values (5, 7 and
9) at room temperature. The pH was adjusted
using diluting aqueous NaOH (pH 13.0) and
HCl (pH 1.0). Then, Qmax with pH was
studied.

3. Results and Discussion

3.1. Synthesis of semi- interpenetrating polymer
network preparation (in the presence of castor
Oil) [S-IPNC]

The superabsorbent hydrogels were synthesized using

a free-radical polymerization, by various steps like
initiation, propagation and termination of acrylate
monomer (AA) and DMAEMA on carboxymethyl
cellulose (CMC) and castor oil in the presence of
crosslinking agents (MBA). The polymerization
reaction was first initiated by potassium persulfate
(KPS), which acts as a redox initiator.
The steps of S-IPNC formation are shown in scheme
(1) (supplementary file).
The reaction is initiated by anion-radical generation
through thermal decomposition of KPS. The –OH
and -CH2 groups are the active sites for grafting to
occur. Hydrogen was extracted from –OH groups
present in CMC and castor oil using free sulfate Fig. (1): ATR- FTIR of (a) Semi-interpenetrating polymer
anion radicals, leading to the formation of active networks (S-2IPN) ,(S-3IPN) and (S-4IPN) with a ratio of acrylic
alkoxy radicals [42]. Then AA and DMAEMA acid (AA) to dimethyl aminoethyl methacrylate (DMAEMA) (1:2)
, (1:3) and (1:4) respectively, (b) Semi-interpenetrating polymer
monomers were grafted onto CMC and castor oil networks (S-2IPNC) ,(S-3IPNC) and (S-4IPNC) with a ratio of
backbones that containing radical active sites, leading acrylic acid (AA) to dimethyl aminoethyl methacrylate
to the propagation of new polymer chains. Through (DMAEMA) (1:2) , (1:3) and (1:4) respectively and ratio of castor
propagation, pendant –CH=CH2 of MBA reacts with oil to carboxymethyl cellulose (CMC) (1:2) .
polymeric chain and so a crosslinked network
A broad band shows up at 3400–3300 cm−1, related to
structure (S-IPNC) is formed [43, 44]. Hence, a
the O-H stretching. Sharp and intense groups appear
mixture of crosslinked (CMC/AA) IPNC and
uncrosslinked PDMAEMA chains are formed as at 2920 cm−1 and 2850 cm−1, attributed to asymmetric
PDMAEMA chains were interpenetrated through S- and symmetric C-H stretching for -CH3 and -CH2
IPNC. separately. Amide I band appears around 1700 cm–1
due to amidic C=O stretching. Water acts as a proton
3.2.Structural characterization of S-IPN donor to the C=O group. The band at 1605 (1595)
samples using ATR-FT-IR and Raman cm-1 is characteristic of the aqueous solution and
spectroscopy assignable to dihydrogen-bonded C=O groups with
water molecules weakened by the steric hindrance of
We have thought that vibrational spectroscopy is a the polymer chains [45]. Another remarkable peak is
powerful tool to explore molecular Interactions 1580 cm-1, related to the asymmetric stretching of
between a solvent molecule and a target functional carboxylate groups (COO-), which means that some
group incorporated into a polymer chain. of the COO- groups of the polymer are not included
The spectra are fundamentally described by aliphatic in the crosslinking reaction. The ATR-FTIR results
and polysaccharide groups. The ATR-FTIR spectra showed shifts in the carboxylic and amide groups,
indicating the presence of hydrogen bondings within
the IPN formation.
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methacrylate (DMAEMA) (1:2) , (1:3) and (1:4) respectively and

ratio of castor oil to carboxymethyl cellulose (CMC) (1:2) .
Another remarkable band occurs in the spectra
This sharp peak in the region 1300-1500 cm-1 is
around 1315 cm−1, attributed to out-of-plane C-H
due to the methyl group. The high intensity of
bending (methylene twisting/wagging) in aliphatic the peak is proportional to the increased number
chains. In all ATR spectra, a band shown at 1150 of methyl groups in the molecule, which
cm−1 because of the glycoside C-O-C extending of subsequently increases by increasing
polysaccharides and a characteristic peak shows up at DMAEMA concentration. Our finding runs
around 1050 cm-1 due to -N(CH3)2 group in parallel to Roy et al., who observed a near to
DMAEMA. It is evident that the same peaks increase linear increase of the weight ratio with time and
with increasing the concentration of the monomer. monomer conversion for both monomer
Raman spectra of prepared polymer networks are concentrations, suggesting that the weight ratio
shown in Fig.2. With Careful investigation of the could be predicted depending on the monomer
provided spectra, one can see that the main difference concentration [46]. The low-wavenumber
appears in the spectrum of S-4IPNC, where the ratio component arises from the hydrogen bond
of DMAEMA is double-fold than the amount present between molecules. In contrast, the high-
in S-2IPNC. wavenumber component is due to a non-
hydrogen bonded monomer because of the
formation of the intermolecular C=O---H-N
hydrogen bond in the liquid [47].

For S-2IPNC as an example, the -CH3 peak appears

at 310 cm-1 while peaks at 464 cm-1 and 567 cm-1 are
related to symmetric and anti-symmetric N(CH3)2,
respectively. The band of -CH2 rocking appears at
888 cm-1 while for -CH wagging and rocking motions
show at 1091 cm-1.The peak appears at 1286 cm-1 is
assigned to a mixed-mode consisting of the C-N
stretching and the C-C stretching modes.
In the region 1400-1700 cm-1.One notices a
significant shift for the symmetrical mode of
deformation CH3 to be at 1438 cm-1 [48]. The C=C
vinyl stretching mode is usually found in the area of
1660-1610 cm-l[49]. Unfortunately, the high Rayleigh
diffusion, which arises from heterogeneity dielectric,
prevents analysis of the area below 200 cm-1.
Hydration leads to shifting in wavenumber,
especially the elongation mode C = O, very sensitive
to hydrogen bond formation O…X: the formation of
hydrogen bond elongates and then weakens the C=O
bond, referring to the literature [45, 47, 49].

3.3. Thermogravimetric analysis

Fig.3 illustrates the thermal properties of the prepared
polymer networks. The data reveal that the thermal
degradation for all the prepared hydrogel started
above 200 oC. The data for weight loss as obtained by
Fig. (2): Raman spectroscopy of (a) Semi-interpenetrating
polymer networks (S-2IPN) ,(S-3IPN) and (S-4IPN) with a ratio
the TGA are shown in Table 2.
of acrylic acid (AA) to dimethyl aminoethyl methacrylate
(DMAEMA) (1:2) , (1:3) and (1:4) respectively, (b) Semi-
interpenetrating polymer networks (S-2IPNC) ,(S-3IPNC) and (S-
4IPNC) with a ratio of acrylic acid (AA) to dimethyl aminoethyl

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Almost S-IPN and S-IPNC samples show thermal 3.4. Phase morphology using a scanning
stability up to 200 oC, about 20% weight loss occurs electron microscope
in the range 200 oC - 250 oC due to the dehydration of The morphology of S-3IPN is shown in fig. (4 and
molecules and the removal of volatile and/or smaller 4b) and S-3IPNC samples are shown in 4c, 4d,4e, 4f
groups of materials [34]. 70% weight loss for all before and after swelling respectively, at different
samples occurs up to 400 oC due to the microscales at (100 μm and 50 μm). SEM images of
decomposition of DMAEMA moieties. Hence, S-3IPN showed that interconnection pores appear due
thermogravimetric analysis showed that a higher to the incorporation of CMC into the polymer matrix
concentration of castor oil improved the thermal using interfacial adhesion force that enhances the
resistance as the hydrogel, which have castor oil in reinforcement effect. Also, the morphology of S-
their backbone, is more stable than its counterparts. 3IPNC shows the formation of a strong network
formed by hydroxyl groups in CMC and castor oil,
which forms a hydrogen bond with PDMAEMA
and/or AA. After swelling, the absorption process
fills up the pores that can be observed from SEM
images 4c,4d,4e,4f where pores are filled up and
surface morphology is now smooth after absorption.
Furthermore, SEM images show a regular
distribution of pores with size variation and approved
that the interpenetrating polymer network was formed
effectively.

Table (2): TGA data corresponding to fig. (3).

Sample Temperature Temperature Temperature

Name (oC)/Wt. loss% (oC) /Wt. loss% (oC) /Wt. loss%
S-2IPN 230 oC/ 20% 360 oC /55% 497 oC / 69%
S-2IPNC 242 oC/ 20% 510 oC/ 74% ________

S-3IPN 199 oC / 24% 308oC/ 61% 460 oC / 74%

S-3IPNC 213 oC / 18% 483 oC / 78% ________
S-4IPN 225 oC / 33% 335 oC /57% 479 oC / 70%
S-4IPNC 210 oC/ 22% 469 oC / 78% ________

3.5. Atomic force microscope:

The surface topography of the prepared polymer
networks in the 3D image is illustrated in Fig. (5a)
and (5b), respectively. All samples showed a granular
morphology that characterizes crosslinked CMC/Poly
(AA-DMAEMA) polymer network, which is
stabilized by hydrogen bonds formed between polar
groups of CMC and functional groups of
PDMAEMA and/or AA that confirmed with ATR-
FTIR studies. The porous structure of the
interpenetrating polymer network is very
Fig. (3): TGA of the prepared hydrogels (a): Semi-interpenetrating pronounced, as confirmed before using SEM. Fig.
polymer networks (S-2IPN) and (S-2IPNC) with a ratio of (5a) exhibited a coarse morphology with an irregular
acrylic acid (AA) to dimethyl aminoethyl methacrylate interconnected granular feature, which became
(DMAEMA) (1:2) and castor oil to carboxymethyl cellulose
polished after adding castor oil, as shown in Fig.
(CMC) (1:2) in case of S-2IPNC, (b):Semi- interpenetrating
(5b). Moreover, there is an obvious amorphous
structure with more uniform crosslinking between
polymer networks (S-3IPN) and (S-3IPNC) with a ratio of acrylic
polymeric chains. The incorporation of castor oil
acid (AA) to dimethyl aminoethyl methacrylate (DMAEMA) (1:3)
increases the spacing between chains and diminishes
and castor oil to carboxymethyl cellulose (CMC) (1:2) in case of
the porosity. The presence of visible pores approves
S-3IPNC and (c) Semi-interpenetrating polymer networks
the superabsorbent feature of samples [50] while
(S-4IPN) and (S-4IPNC) with a ratio of acrylic acid (AA) to
fig.(5c,5d) show the swelling state of S-3IPN,S-
dimethyl aminoethyl methacrylate (DMAEMA) (1:4) and castor 3IPNC respectively as S-3IPNC shows a fully
oil to carboxymethyl cellulose (CMC) (1:2) in case of S-4IPNC. swollen structure with high water uptake as pores

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were shown to be filled with water molecules and

eventually pores dimensions increase, unlike S-3IPN
which shows a partially swollen network. While fig.
(5e, 5f) show the de-swelling state of S-3IPN, S-
3IPNC respectively as 3IPNC shows a steady
network structure, holding water molecules into their
pores despite 3IPN which shows a rapid water release
that leads to deformation in the topography of 3D
polymer network and increasing the size of cavities
into a network structure.

Fig. (5): AFM of (a) Semi-interpenetrating polymer networks (S-

3IPN) with a ratio of acrylic acid (AA) to dimethyl aminoethyl
methacrylate (DMAEMA) (1:3) and (b) Semi- Interpenetrating
polymer network (S-3IPNC) with a ratio of acrylic acid (AA) to
dimethyl aminoethyl methacrylate (DMAEMA) (1:3) and ratio of
castor oil to carboxymethyl cellulose (CMC) (1:2) at 2.5 µm
respectively, (c, d) swelling state of (S-3IPN) and (S-3IPNC)
at 2.5 µm respectively and (e,f) de-swelling state of (S-3IPN) and
(S-3IPNC) at 2.5 µm respectively.

3.6. X-ray Diffraction:

Fig. (4): SEM of (a,b) Semi-interpenetrating polymer networks (S- X-ray diffraction (XRD) is commonly used to
3IPN) with a ratio of acrylic acid (AA) to dimethyl aminoethyl determine whether the materials are crystalline or
methacrylate (DMAEMA) (1:3) at 100μm and 50μm respectively amorphous. Intense and sharp peaks in the diffraction
and (c,d) Semi-Interpenetrating polymer network (S-3IPNC) with
a ratio of acrylic acid (AA) to dimethyl aminoethyl methacrylate
pattern of a sample are characteristic of crystalline
(DMAEMA) (1:3) and ratio of castor oil to carboxymethyl materials, while amorphous materials show no
cellulose (CMC) (1:2) at 100μm and 50μm respectively and (e,f) intense peaks. XRD patterns of S-2IPN, S-2IPNC, S-
swelling state of (S-3IPNC) at 100μm and 50μm respectively. 3IPN, S-3IPNC, S-4IPN, and S-4IPNC samples are
shown in Fig. (6) indicate having amorphous
properties due to low intense peaks and wide halos.
AFM figures coincide with TGA and cycles of The patterns of S-3IPN and S-3IPNC show peaks
swelling-deswelling of IPN samples and confirm the
between 2Ө values of 28-59 0, which indicate grafting
importance of castor oil in IPN hydrogels which is
of poly (DMAEMA) on CMC. That shows the
considered as a promising green component that
enhancement of crystallinity in the superabsorbent
achieves a pioneering role in enhancing a network composite.
structure with a constant arrangement and high
internal stability

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7458 Alaa I. E. Abdelaziz et.al.
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materials to change its hydrophilic nature when the

temperature approaches the LCST as shrinkage
occurs and swelling decreases due to phase
separation. According to the temperature where
hydrogel releases it is half of the absorbed water
(LCST) occurs at 35oC, as LCST of PDMAEMA
showed in the range of 32–55 0C [52, 53].

Table (3): Swelling ratio percentage of prepared hydrogels

Sample Qmax(g/g) SR% No. of Conditions

Fig. (6): XRD of Semi-interpenetrating polymer networks(S- Code cycles
2IPN) ,(S-2IPNC) with a ratio of acrylic acid (AA) to dimethyl S-4IPNC 208.348 g.g-1 20734.8% 6 25oC, 0M,
aminoethyl methacrylate (DMAEMA) (1:2) , (S-3IPN) , (S- pH7
-1
3IPNC) with a ratio of acrylic acid (AA) to dimethyl aminoethyl S-3IPNC 191.21g.g 19021% 6 25oC, 0M,
methacrylate (DMAEMA) (1:3) , (S-4IPN) and (S-4IPNC) with pH7
a ratio of acrylic acid (AA) to dimethyl aminoethyl methacrylate S-2IPNC 175.82 g.g-1 17482% 6 25oC, 0M,
(DMAEMA) (1:4) as ratio of castor oil to carboxymethyl pH7
cellulose (CMC) (1:2) in case of S- 2IPNC,S-3IPNC and S-4IPNC. S-4IPN 159.35 g.g-1 15835% 5 25oC, 0M,
pH7
S-3IPN 145.21 g.g-1 14421% 5 25oC, 0M,
pH7
4. Factors affecting on swelling properties S-2IPN 123.82 g.g-1 12282% 5 25oC, 0M,
pH7
4.1. Effect of temperature:In order to investigate the
effect of temperature on swelling behavior, the other
parameters are kept constant (pH 7 and 0 M salt 4.2. Effect of salt: The maximum water absorption
concentration). The maximum water absorption (Qmax) was monitored for the investigated hydrogels
(Qmax) of the prepared hydrogels, namely, S-2IPN, at different NaCl saline solutions (0.2 M, 0.6M and
1M) keeping other variables constant, i.e., 25 oC and
S-3IPN, S-4IPN, S-2IPNC, S-3IPNC and S-4IPNC
pH 7. It is observed from fig. (7b) that prepared
were measured as a function of temperature within hydrogels are salt responsive, i.e., the Q max for all
the range of 25-45 oC, Fig. (7a). The maximum water the investigated hydrogels decreases with increasing
absorbance was achieved nearly after 2hrs. The salinity of the absorbed water. For instant, when
temperature / Qmax curves show that the investigated salinity increases from 0.2 M to 1 M i.e., 5 folds. The
hydrogels respond effectively to the temperature and Q max of S-4IPNC has reduced from (192.8g/g) to
release the absorbed water when approaching their (178.2 g/g). While Qmax of S-2IPN was (136.7 g/g)
at 0.2M. The swelling behavior of hydrogels in a salt
LCST, which proves their usability under different
solution can be explained by the interaction between
environmental conditions. The data revealed that the fixed ions on the hydrogel and mobile ions, which are
order of water absorption is as follows: S-4IPNC, S- affected by the salt concentration and the osmotic
3IPNC, S-2IPNC, S-4IPN, S-3IPN and S-2IPN pressure. As the fixed ions on hydrogel attract mobile
respectively as shown in table (3). It can be seen that- charges in the environmental solution that leads to an
beyond a certain temperature- the rate of swelling imbalance of ions concentration between the
hydrogel and outer solution, and finally, the
decreases sharply (above the LCST the network
deformation of hydrogel occurs [54, 55]. At a high
becomes more compact and the interpenetration of salt concentration of NaCl solution, Qmax decreases
the water into the network comes to be very difficult) due to decreasing in Donnan osmotic pressure as the
Also, it is clear that the swelling is more efficient competitive effect of the ions of the salt on the active
upon increasing the weight ratio of DMAEMA to the sites with the water molecules occurs. The difference
acrylic acid i.e. (S-4IPNC). This improvement in the between the concentration of Na+ and Cl- ions in the
swelling is due to that the presence of carboxylic external and swelling medium decreases, which
subsequently leads to decrease hydrogel swelling
groups which increase electrostatic repulsion between
[56].
the carboxylate ions-COO-) [51] The swelling 4.3. Effect of pH:
behavior of the hydrogels can be explained by the The effect of pH on the swelling properties of S-
following assumption: the bonding of 2IPN, S-3IPN, S-4IPN, S-2IPNC, S-3IPNC and S-
Carboxymethylcellulose (CMC) to polyacrylamide 4IPNC is shown in Fig. (7C) at pH values 5, 7 and 9.
(PAAm), a hydrophilic material, promotes these As the prepared hydrogels are composed of
interpenetrating polymer networks based on carboxyl
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methylcellulose and two crosslinked polymers, one of

them is thermoresponsive, and the other is pH-
responsive to achieve the dual function. An increase
in swelling ratios from pH (5-7) was observed and
then a sharp decrease in water uptake was observed
from pH (7-9). In the acidic medium (At pH > 4), the
osmotic pressure inside the hydrogel increases lead to
higher swelling because of the dissociation of
carboxyl groups that exist in hydrogels. While at pH
> 7, i.e., basic medium, the concentration of basic
cations in the outer solution increases and a further
amount of mobile ions increases which leads to
decrease osmotic pressure and eventually reducing
water absorption [57].
For an instant, when pH increases from 5 to 7. The Fig. (7) : Water absorption for semi-interpenetrating polymer
networks (S-4IPN) ,(S-3IPN) , (S-2IPN) with a ratio of acrylic
Qmax of S-4IPNC has increased from (191.5 g/g) to acid (AA) to dimethyl aminoethyl methacrylate (DMAEMA) (1:4)
(208 g/g) then back to reduced when pH reaches 9. , (1:3) and (1:2) respectively and semi-interpenetrating polymer
While Qmax of S-2IPN was (123.8 g/g) at neutral network (S-4IPNC) ,(S-3IPNC) , (S-2IPNC) with a ratio of
medium. acrylic acid (AA) to dimethyl aminoethyl methacrylate
(DMAEMA) (1:4) , (1:3) and (1:2) respectively and ratio of castor
The incorporation of a long chain of castor oil within oil to carboxymethyl cellulose (CMC) (1:2) under a) effect of
the network affords the network structure with temperature (b) effect of salinity and (c) effect of pH.
flexibility and increases the size of the pores
available for water capturing. Therefore, the samples 5. Re-swelling capability of interpenetrating
with castor oil incorporated inside their 3D structure network hydrogel
showed higher swelling in comparison to their Swelling-deswelling capability is one of the most
counterparts. Up to our knowledge, it is the first time important parameters judging the workability of
to include castor oil in such formulations; therefore, hydrogels in agricultural areas[58]. The water
there are no data available to compare our data with. absorbency of the interpenetrating network hydrogel
structures in distilled water as a function of the
number of reswelling times is shown in Fig. 8. The
swelling capacity of hydrogel samples gradually
decreases with increasing the number of reswelling
cycles as S-IPNC hydrogels show 6 cycles as Qmax
starts to increase gradually from 208.348 g/g
(20734.8%) in 1st cycle then decay in 6th cycle to be
95.138g/g (9413.8%). While S-IPN hydrogels show
5 cycles as Qmax start to increase gradually from
123.82 g/g (12282% ) in 1st cycle then decay in 5th
cycle to be 32.315 g/g (3131.5%) as shown in table
(3). This is probably due to the breakage of physical
crosslinking points of S-IPN networks in the
repeating process of swelling-reswelling, causing
severe damage to polymeric network structures [59].
Therefore, the ability of the hydrogel for holding
water is gently diminished and the equilibrium water
absorbency is decreased consecutively. This result
displays that the S-IPN hydrogel has maintained at a
certain degree of swelling capability after reused for
several cycles. Therefore, the obtained
interpenetrating network hydrogels could be used as
reusable and recyclable materials in many fields.
Moreover, it is shown that increasing concentration
of the hydrophilic monomer DMAEMA into
interpenetrating network hydrogel significantly
enhances the reswelling capability of the network.
Finally, table (3) show that S-4IPNC was the highest
water absorbance and S-2IPN was the lowest one.

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7460 Alaa I. E. Abdelaziz et.al.
_____________________________________________________________________________________________________________

lowest Qmax (136.7g/g). This Phenomenological

occurrence can be attributed to the effect of the
additional cations which cause a decrease in anion–
anion electrostatic repulsion, resulting in a decrease
in the osmotic pressure difference between the
polymer networks and the external solution. The
difference in mobile ion concentration between the
polymer networks and liquid phases decreases
resulting in a decrease in absorbency capacity [60,
61]. Regarding pH, at neutral medium, S-4IPNC and
S-3IPNC show the highest maximum water
absorbance (208 g/g) and (191 g/g) respectively
Fig. (8): cycles of swelling-deswelling for semi-interpenetrating while S-2IPN show the lowest Qmax (123.8 g/g ) as
polymer networks (S-4IPNC) ,(S-3IPNC) ,(S-2IPNC) with a ratio shown in table (3). While in acidic conditions below
of acrylic acid (AA) to dimethyl aminoethyl methacrylate
(DMAEMA) (1:4) , (1:3) and (1:2) respectively and ratio of castor
6 or basic conditions of above 8 generally lowered
oil to carboxymethyl cellulose (CMC) (1:2) and (S-4IPN) ,(S- the swelling ratio with a favourable ratio in the range
3IPN) , (S-2IPN) with a ratio of acrylic acid (AA) to dimethyl of 6-8 being identified. The results show that high
aminoethyl methacrylate (DMAEMA) (1:4) , (1:3) and (1:2) temperature above 40°C, high salt concentration(1M)
respectively .
and basic medium at pH=9 usually result in a
6. Mechanism of water release from swelling collapse of the 3-D network structure. The
hydrogels phenomena of water absorption and desorption are
The hydrophilic groups present in the polymer e.g. shown in Fig. (9).
(acrylamide, carboxylic acid, etc.) are in charge of
water absorption in hydrogels. These hydrophilic
groups are attached to the chain of the polymer. Upon
interaction between 3D polymer network structure
and water molecules, several negative COO- groups
appeared and repel each other and finally the chain
opened up, also numerous hydrogen bondings occur
between –COO- groups, –NH groups and water
molecules causing more water absorption and more
swelling. These bondings are disturbed under the
effect of the environmental changes such as
temperature, salinity and pH, that lead to a release of
some water molecule and shrinkage of polymer
network consequently happens.
At 25 °C, for S-4IPNC, S-3IPNC, the polymer
network formed hydrogen bonds with the water
molecules, developing a hydration shell around the
hydrophilic group which enhanced water uptake
capacity to high absorbency (208 g/g) and (191 g/g)
respectively while S-2IPN show the lowest Qmax
(123.8 g/g ). However, with increasing temperature,
the absorbency steadily decreased due to the
elasticity of the cross-linked polymer network
leading to the release of absorbed water. The collapse
of the hydration shell at high temperature may be
responsible for the decrease in absorbency capacity.
The polymer 3D network structure collapses due to
destabilization of the polymer network structure,
under different factors as Temperature, pH and salt
medium, leading to synerisis[60]. In a salty medium,
for S-4IPNC, S-3IPNC the maximum water Fig. (9): Mechanism of absorption-desorption process.
absorbance was observed at low sodium salt
concentration (0.2M) to reach (192.8g/g) and (178
g/g) respectively, then it decreases subsequently in
high NaCl concentration while S-2IPN show the
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 PREPARATION AND CHARACTERIZATION OF A NEW FAMILY OF BIO-INTERPENETRATING.... 7461
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‫تحضيروتوصيف عائلة جديدة من شبكات الهيدروجيل المتداخلة البينية بواسطة طريقة‬

‫خضراء‪.‬‬
‫آالء ابراهيم السيد عبد العزيز ‪ , 1‬شيماء محمد السعيد‪ , 1‬السيد جمال ذكى‪ ,1‬محمد محمود محمد أبو على‪, 2‬منارالسيدعبدالرءوف‪ , 1‬أحمد محمد‬
‫‪1‬‬
‫الصباغ‬

‫‪ 1‬معهد بحوث البترول‪ 1 ,‬شارع أحمد الزمر‪ -‬حى الزهور‪ -‬مدينة نصر‪-‬القاهرة – مصر‪.‬‬
‫‪ 2‬قسم الكيمياء ‪ --‬كلية العلوم‪ -‬جامعة عين شمس‪-‬القاهرة‪ -‬مصر‪.‬‬
‫في هذا البحث يتم تحضير شبكات البوليمرات المتداخلة فى وجود و غياب زيت الخروع‬
‫)‪(S-2IPNC, S-3IPNC, S-4IPNC, S-2IPN, S-3IPN and S-4IPN‬عن طريق عملية بلمرة الشقوق الحرة فى وجود كال من حمض األكريليك‬
‫كمونومر مستجيب لألس الهيدروجيني وثنائي ميثيل إيثيل ميثاكريالت كمونومر مستجيب للحرارة وكربوكسى ميثيل السليلوز كمشتق سليلوزى وكذلك البوتاسيوم‬
‫بيرسلفات والميثيلين بيساكريالميد‪ .‬يتم دمج زيت الخروع كمادة كيميائية خضراء بنسبة (‪ )2 :1‬إلى الكربوسى ميثيل سليلوز‪.‬‬
‫تم تحضير شبكات البوليمر المتداخلة وتوصيفها بواسطة تقنيات مختلفة مثل األشعه تحت الحمراء وأشعة الرامان الطيفي لدراسة تركيبها الكيميائى وكذلك تحليل‬
‫الثبات الحرارى والميكروسكوب االلكترونى الماسح واألشعة السينية وميكروسكوب القوة الذرية لدراسة كال من التحليل الحراري الوزني ‪ ،‬وتضاريس السطح ‪،‬‬
‫والتبلور‪ ،‬وطبوغرافيا السطح ‪ ،‬على التوالي‪ .‬وأثبت الدراسات ان إضافة زيت الخروع يعززمن نسيج وثبات الهيدروجالت‪ .‬وتشير نتائج الدراسات الى أن ‪S-‬‬
‫من‬ ‫أعلى‬ ‫امتصاص‬ ‫قدرة‬ ‫يظهر‬ ‫‪IPNC‬‬
‫‪ S-IPN‬عند تركيزات منخفضة من كلوريد الصوديوم وفى نطاق األس الهيدروجيني (‪ )7-5‬وذلك بسبب زيادة الضغط األسموزى‪ .‬لذلك ‪ ،‬يمكن استخدام زيت‬
‫الخروع كمادة خضراء في شبكات البوليمرالمتداخلة وتطبيقها لتوفيرالمياه وبذلك تمتلك الهيدروجيالت البينية إمكانية كبيرة لتخزين المياه الستخدامها في المجال‬
‫الزراعي‪.‬‬

‫________________________________________________‬
‫)‪Egypt. J. Chem. 64, No. 12 (2021‬‬

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