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Superabsorbent polymer composites derived from polyacrylic acid: Design

and synthesis, characterization, and swelling capacities

Article  in  Polymers and Polymer Composites · June 2020

DOI: 10.1177/0967391120933482

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Article
Polymers and Polymer Composites
1–7
Superabsorbent polymer composites ª The Author(s) 2020
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derived from polyacrylic acid: Design sagepub.com/journals-permissions

DOI: 10.1177/0967391120933482
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and synthesis, characterization, and
swelling capacities

Marzieh Jafari, Gholam Reza Najafi , Mahboubeh A Sharif

and Zahra Elyasi

Abstract
Superabsorbent polymers (SAPs) were synthesized by aqueous solution polymerization of carboxymethyl cellulose
(CMC)/acrylic acid (AAc) and polyvinyl alcohol (PVA)/AAc blend using benzoyl peroxide as an initiator. SAPs were
synthesized by a facile method under mild conditions. A comparative study was done between CMC/AAc as a biode-
gradable superabsorbent and PVA/AAc copolymer. The effects of cross-linking, reaction time, temperature, and initiator
molar ratio on water absorbency were studied herein. The highest swelling capacity was obtained for CMC/AAc bio-
degradable superabsorbent composite. The water absorption capacity of SAPs increased with increases in benzoyl
peroxide content, immersion time, and reaction temperature of polymerization. The gel fraction of SAPs decreased with
increases in the amounts of N,N0 -methylenebisacrylamide as a cross-linker. Fourier-transform infrared spectroscopy was
used to examine the molecular interactions. The morphology and structure of superabsorbent composites were inves-
tigated by scanning electron microscopy.

Keywords
Superabsorbent polymer, polyvinyl alcohol, carboxymethyl cellulose, acrylic acid, gel fraction, swelling capacity

Received 24 April 2019; accepted 22 March 2020

Introduction
Superabsorbent polymers (SAPs) can be described as having a three-dimensional, hydrophilic network systems and a
moderate degree of cross-linking with the ability to absorb water considerably greater than their dry mass.1–3 The SAPs
contain carboxylic acid, partially neutralized carboxyl groups, carboxylate salt, and carboxamide. They draw surrounding
water into the network by diffusion while the SAPs backbone chains maintain their structure due to cross-linking, so the
polymer network expands and swells. Also, the covalent cross-links can prevent the polymer network from being
dissolved in water. They are able to absorb water without dissolving, exceeding 1000- to 1500-fold their dry weight.4–11
Due to such significant properties, the SAPs are produced for different applications. For example, they are used in
disposable baby diapers,12,13 agriculture as soil amendments,14,15 coal dewatering,16 controlled release of drugs as
carriers,17,18 cosmetics19 and absorbent pads, and wastewater treatment.20,21
The structure of polyacrylic acid contains an ionizable group on each repeat unit (–COOH). These chains are then
cross-linked. SAPs are prepared from acrylic acid (AAc) and a cross-linker by suspension or solution polymerization.22–24
The type and amount of cross-linker control both the stretchability and swelling capacity.
SAPs are classified into three types, namely semi-artificial (cellulosic derivatives), synthetic polymers, and natural
(polysaccharide derivatives). Demand has arisen for natural polymer-based superabsorbent materials that are derived from
feedstock such as cellulose.25–28

Department of Chemistry, Qom Branch, Islamic Azad University, Qom, Iran

Corresponding author:
Gholam Reza Najafi, Department of Chemistry, Qom Branch, Islamic Azad University, Post Box: 37491-13191, Qom, Iran.
Email: najafi@qom-iau.ac.ir
2 Polymers and Polymer Composites XX(X)

Compared to synthetic petroleum-based polymers, these polymers have the advantages of sustainability, high hydro-
philicity, nontoxic base components, and biodegradation properties. Natural polymers can be made from carboxymethyl
cellulose (CMC), which has a naturally occurring polysaccharide cellulose base.29
Feng Cheng et al. reported that the mechanical properties of polyvinyl alcohol (PVA) were improved by incorporating
PVA-grafted graphene oxide.30
Ali Akl et al. synthesized PVA core and poly(N-isopropylacrylamide/acrylic acid) shell.31
In this study, biodegradable CMC was chosen instead of graphene oxide or other chemical component. The SAPs were
synthesized by grafting polyacrylic acid onto CMC and PVA via solution copolymerization.
Synthesized superabsorbents were also compared in terms of the polymerization conditions along with investigating
their effects on absorbency. Fourier-transform infrared (FTIR) spectra were used to characterize successful graft copo-
lymerization. The morphology and structure of superabsorbent composites were investigated by scanning electron micro-
scopy (SEM).

Experimental
Materials
AAc of 99.8% purity, benzoyl peroxide, CMC (AR grade), sodium hydroxide, and N,N0 -methylenebisacrylamide (MBA)
(AR grade) were purchased from Aldrich (Singapore), E-Merck, Merck KGaA Corporate (Frankfurter strabe, Germany),
and Fluka (Buchs SG, Switzerland), respectively, the two latter of which were used in alkaline hydrolysis and as cross-
linker, respectively. PVA and reagent grade ethanol were procured from Aldrich Chemical Co. and E-Merck, respectively.

Preparation of superabsorbents
As shown in Figure 1, AAc (7.2 g) was dissolved in 15 ml distilled water/ethanol solution and then neutralized with
sodium hydroxide solution (2 M) in a three-neck round bottom flask reactor. Then, benzoyl peroxide, CMC (0.01 g), and
MBA (0.15 g) as cross-linkers were added and stirring was continued under reflux condition to dissolve them. Polymer-
ization reaction was carried out for 15 min while keeping the reaction temperature at 90 C. Finally, the resulting product
was washed several times with distilled water, and dried at 60 C to a constant weight, followed by then screening.
The reaction was repeated for AAc (7.2 g), benzoyl peroxide, MBA (0.15 g), and PVA (0.01 g) at the same condition.
Polymerization reaction was carried out for 25 min.

Water absorbency measurement

A weighed quantity of the SAPs was immersed in distilled water at room temperature (approximately 27 C) to reach the
swelling equilibrium. Swollen samples were then separated by screening and weighed after being drained on a sieve for 15
min. The experiment was repeated for each sample, to determine its average weight. The swelling ratio was calculated
using the following equation
Water absorption ð DSÞ ð%Þ ¼ W 2  W 1 =W1  100
where W2 and W1 are the weights of the water-swollen sample and the dry sample, respectively.

FTIR spectrum and SEM analysis

Infrared absorption spectra of samples were studied using IR Prestige-21 Shimadzu (Shimadzu Co., Japan). The SAPs
were mixed with KBr and pressed to a plate for spectrometric measurements from 4000 cm1 to 400 cm1 at room
temperature. A background spectrum containing no sample was subtracted from all spectra. The SEM images were
recorded on a Zeiss Supra 40 (Germany) at an acceleration voltage of 5 kV.

Results and discussion

FTIR spectroscopic analysis
FTIR spectroscopic analysis was used to determine the nature of the bond formation. Pure CMC had absorption bands
related to O–H stretching at 3498 cm1, carbonyl stretching in the anhydroglucose unit of the cellulose at 1591 cm1,
–CH2– stretching at 2951 cm1, C–OH at 1408 cm1, and C¼O stretching from an asymmetric oxygen bridge at
1178 cm1. As shown in Figure 2, the absorption bands of CMC were obviously weakened after the reaction in the
CMC/AAc blend hydrogel. In spectrum (b), the new band at 1759 cm1 (carbonyl stretching of –COOH groups) showed
the carbonyl group of AAc, which was absent in spectrum (a). The band shift apparent at 1599 cm1 (at 1591 cm1) for
CMC/AAc SAPs indicates the formation of SAPs.
Jafari et al. 3

Figure 1. Schematic representation of synthesis of CMC/AAc SAP.

CMC: carboxymethyl cellulose; AAc: acrylic acid; SAP: superabsorbent polymer.

Figure 2. Infrared spectroscopy of (a) pure CMC powder and (b) CMC/AAc SAP.
CMC: carboxymethyl cellulose; AAc: acrylic acid; SAP: superabsorbent polymer.

Grafting of AAc and PVA was confirmed by FTIR studies. In pure PVA (Figure 3(a)), characteristic peaks appear at
3379 and 2943 cm1, respectively, for the O–H and C–H stretching vibrations, whereas the bands appearing at 1441 and
1097 cm1 are due to C–H and O–H bending vibrations, respectively. Appearance of a new band at 1724 cm1 for PVA/
AAc along with other bands confirms the formation of a graft copolymer.

SEM analysis
Two samples were chosen with different amounts of initiators, and their morphologies were examined by SEM. Figure 4
shows morphological images of CMC/AAc with initiator amounts of (a) 0.1 g and (b) 0.7 g. The result showed that the
morphology in Figure 4(a) was less porous and thus more compact than that in Figure 4(b) which confirms the results of
swelling analysis showing that sample (a) has less value than the other. The initiator, therefore, affected both the length of
the polymer chains and the morphology and molecule weight. Excessive overgrowth of the initiator causes very high
branching as a result of small cavities.
4 Polymers and Polymer Composites XX(X)

Figure 3. Infrared spectroscopy of (a) pure PVA powder and (b) PVA/AAc SAP.
PVA: polyvinyl alcohol; AAc: acrylic acid; SAP: superabsorbent polymer.

Figure 4. SEM of CMC/AAc copolymer with initiator amounts of (a) 0.1 g and (b) 0.7 g.
SEM: scanning electron micrograph; CMC: carboxymethyl cellulose; AAc: acrylic acid.

Effect of initiator contents on the water absorbency

With the aim of investigating the effect of initiator contents on the water absorbency, samples obtained from five different
amounts of benzoyl peroxide were subjected to equilibrium swelling measurements in distilled water. Figure 5 shows that
the water absorbency for samples increased with the increasing benzoyl peroxide content. The initiator, therefore, affected
the length of the polymer chains and influenced the molecule weight. The increase of initiator amounts will shorten the
chains, thus the produced SAPs will be less hard. As shown in Figure 5(c), maximum value was obtained from the CMC/
AAc SAP sample.

Effect of cross-linker content on the water absorbency

Figure 6 shows the effects of cross-linker dosage on the swelling capacity of samples. It is seen that 0.15 g of MBA
provided the highest swelling capacity, with an overdose giving much poorer swelling. Since the MBA served as a cross-
linker, it increased the cross-linking, which later decreased the ability of water swelling. The increase of network density
also led to increased physical entanglements and decreased swelling property.
Jafari et al. 5

3500

The water absorption rate

3000
2500
2000
A
1500
B
1000
C
500
0
0.1 0.2 0.6 0.8 0.9
Initiator content (g)

Figure 5. Effect of initiator content on the water absorbency in distilled water at room temperature: (a) polyacrylic acid, (b) PVA/AAc
copolymer, and (c) CMC/AAc copolymer.
PVA: polyvinyl alcohol; AAc: acrylic acid; CMC: carboxymethyl cellulose.

3500
The water absorption rate

3000
2500
2000
1500
1000
500
0
0.1 0.15 0.2 0.3
A 1200 1760 1440 980
B 2300 2800 2620 1710
C 2750 3140 2630 1925

Cross linker content (g)

Figure 6. Effect of MBA content on the water absorbency of (a) polyacrylic acid, (b) PVA/AAc SAP, and (c) CMC/AAc SAP at room
temperature.
MBA: N,N0 -methylenebisacrylamide; PVA: polyvinyl alcohol; AAc: acrylic acid; SAPs: superabsorbent polymers; CMC: carboxymethyl
cellulose.

4500
The water absorption rate

4000
3500
3000
2500
2000
1500
1000
500
0
25 40 55 70 85

Temperature (ºC)

A B C

Figure 7. Effect of temperature on the water absorption of (a) polyacrylic acid, (b) PVA/AAc, and (c) CMC/AAc SAPs.
PVA: polyvinyl alcohol; AAc: acrylic acid; CMC: carboxymethyl cellulose; SAPs: superabsorbent polymers.

Effect of reaction temperature on the water absorbency

The influence of the reaction temperature on the swelling capacity was investigated at varying range of 25–90 C and the
results are depicted in Figure 7. The highest water swelling capacity was observed at 75 C. Since a low temperature
reduces the activity of radicals, slows down the decomposition rate of the initiator agent, and impedes the delivery of
polymerization reaction chain, the prepared SAP with a low reaction temperature shows relatively low molecular weight
and water absorbency. As the reaction temperature increased, the conversion ratio of the monomer raised, leading to
increased ability for the absorption of water.
6 Polymers and Polymer Composites XX(X)

Conclusions
In summary, a series of superabsorbent composites was prepared by graft copolymerization based on AAc to investigate
the effect of reaction variables on the swelling capacity. The highest swelling capacity was obtained for CMC/AAc
superabsorbent composite. It was found that the contents of various factors, such as cross-linker amounts, temperature,
and initiator content, had significant influences on the water absorbency. The water absorbency of samples increased with
increasing benzoyl peroxide content as initiator and temperature. The increased cross-linking also decreased the ability of
water swelling. The successful synthesis of SAPs was confirmed by FTIR spectra through comparing absorption peaks
and the morphology of superabsorbent composites by SEM.

Declaration of conflicting interests

The authors declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Funding
The authors disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: This study
was financially supported by the Islamic Azad University, Qom Branch, Iran.

ORCID iD
Gholam Reza Najafi https://orcid.org/0000-0002-2687-3729

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