One-step synthesis of corn starch urea based acrylate

superabsorbents
Ting Guo Liu,1 Yun Tao Wang,2,3 Jun Guo,1 Tian Bao Liu,1 Xin Wang,1 Bin Li2
1
Provincial-Level Experimental and Teaching Demonstration Center of Chemical Materials & Engineering, College of Chemistry &
Materials Engineering, Chizhou University, Anhui Chizhou 247100, People’s Republic of China
2
College of Food Science and Technology, Huazhong Agricultural University, Wuhan 430070, People’s Republic of China
3
School of Food and Biological Engineering, Zhengzhou University of Light Industry, Zhengzhou 450000, People’s Republic of China
Correspondence to: T. G. Liu (E - mail: liutg137@hotmail.com)

ABSTRACT: A one-step synthesis procedure for starch-based acrylate superabsorbent polymers was proposed. The reaction conditions
that may affect the water absorption capacity were discussed. A transparent gel-like polymer containing urea (USAP) was successfully
obtained by dissolving starch in a NaOH solution without further gelatinizing processing and using acrylic acid directly without prior
neutralization. Urea was used as the nitrogen source and pore-forming agent to improve the performance of the USAP. The optimum
reaction conditions of the swelling ratio were also studied. A corn starch USAP was synthesized under the optimum conditions, and
the water absorbency was 2704 6 22, 561 6 39, 100 6 5, and 96 6 4 g/g, respectively, in distilled water, running water, physiological
saline, and artificial urine. Five kinds of starch-based USAPs were also successfully prepared under the same conditions with excellent
water absorption capacities, revealing that the one-step method was a more convenient method for a potential industrial application
pathway. The polymers were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffrac-
tion, and thermogravimetric analysis. The results indicated that the PAA chains were successfully grafted onto the starch backbone.
However, the starch molecular structure was not completely destroyed during the graft polymerization. The thermal analysis and
nitrogen content results proved that urea was also involved in the graft copolymerization. V C 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci.

000: 000–000, 2017

KEYWORDS: copolymers; polysaccharides; resins

Received 8 October 2016; accepted 31 March 2017

DOI: 10.1002/app.45175

INTRODUCTION In order to build a resource-saving society to achieve a sustain-

able economic and social development strategy, biodegradable
Superabsorbent polymers (SAPs) are a class of ultrahigh molec-
polymers have attracted considerable attention because of their
ular weight polymers containing a large number of hydrophilic
distinctive properties, which hopefully alleviate the environmen-
groups with a unique, moderately crosslinked three-dimensional
tal pollution problems caused by using plenty of synthetic poly-
network structure.1 Generally, SAPs are insoluble in water and
mers.5 The green superabsorbent polymers based on
organic solvents, while they can form a hydrogen-bonding
environmentally friendly biomass, including starch (St),1,6 cellu-
structure when in contact with water, which can then absorb
lose,7 chitosan (CTS),8 protein (Pr),9 and some other biological
and retain a large amount of water relative to their own dry
resources10 and their derivatives11 have had wide interest among
weight. Furthermore, the absorbed water is hard to remove
many researchers. Lots of biomass-based SAPs have been
even under some pressure or heating, and the water can be
reported, however, in which the water absorption capacity is
absorbed repeatedly.2 Because of the excellent properties com-
higher in distilled water but poor in practical applications. The
pared to traditional water-absorbing materials, SAPs are widely
salt-tolerant property, gel strength, thermal stability, water
used in many fields, such as agriculture, forestry, desert trans-
retention, and gentle controlled release still need to be further
formation, medicine for drug delivery systems,1,3 food preserva-
improved.12
tion, construction, oil exploration, household chemicals,
environmental protection, and other fields. Especially in the In particular, starch-based hydrogels have been exploited more
fields of physiological health, personal care, and agriculture, frequently and intensively. Graft copolymerization is one of the
SAPs have become one of the indispensable materials.4 most attractive methods for preparing SAP by introducing

C 2017 Wiley Periodicals, Inc.

V

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ARTICLE WILEYONLINELIBRARY.COM/APP
hydrophilic groups onto the original starch backbone.11 Vinyl
monomers, such as acrylic acid (AA), acrylamide (AM), acryloni-
trile (AN), and poly(vinyl alcohol) (PVA), are the most com-
monly used monomers, which can introduce a number of
hydrophilic functionalities like carboxyl or hydroxyl groups in the
copolymers.13 Various methods such as solution polymerization,
inversed phase suspension polymerization, inversed emulsion
polymerization, microwave-assisted synthesis, and solid-phase
ultrasonic synthesis can be successfully implemented in the prep-
aration of SAPs. A variety of initiation methods, including chemi-
cal, gamma-ray radiation, microwave radiation, ultraviolet
radiation, ultrasound, and plasma and electron beams, are used
to initiate the polymerization reaction. Therein, chemical initia-
tion, especially the redox initiation systems, was the most widely
used method.14
Different sources of starch have been used as the grafting skele-
ton, coming from corn,15 wheat,16 potato, sweet potato,17 cas-
sava,13,18 sago,19 amaranthus, and other crops.20 Most native,
granular starches consist of amylose with a linear structure and
amylopectin with a branched structure. The influence of the amy-
lose/amylopectin ratio and molecular chain structure on the
properties of the SAPs has also been extensively studied. Ample
reports show that the properties of starch, such as the native
granular structure, phase transition behavior, and rheological and
functional properties, are different with different amylase con-
tent.21–25 Rath and Singh26 found that amylopectin-g-polyacryl-
amide performed better in flocculation than amylose-g-PAM and
starch-g-PAM. Zou et al.27 prepared a series of biodegradable
starch-based SAPs by grafting acrylamide onto starches that came
from the same source (corn) but with a different amylose/amylo-
pectin ratio. They found that the grafting ratio and efficiency
increased with increasing amylose content, and that the length of
the grafted segment decreased with increasing amylopectin con-
tent. The effects of amylose content of corn starch on the water
absorbence capacity and microstructure of the starch-graft-
sodium acrylate copolymers were also investigated. The grafting
ratio and water absorption increased with decreasing amylose
content, and this is different from the results of Zou et al.27 and
Zhang et al.15 Incomplete gelatinized starch aggregates increased
with increasing amylose content on surfaces and cross sections of
the copolymer.6
Urea is an important raw material used in agriculture, industry,
medicine, laboratory work, and other fields. It is one of the
most commonly used neutral nitrogen fertilizers because it has
the highest nitrogen content, is efficient, and leaves no residue
of harmful substances in the soil. In order to improve the utili-
zation of water resources and fertilizer nutrients to promote the
growth and quality of plants, some ecofriendly polymers such
as wheat straw-g-poly(acrylic acid)28 and flax yarn waste-g-pol-
y(acrylic acid-co-acrylamide)2 superabsorbent composites have
been synthesized, and the sustained-release behavior of urea has
also been evaluated. Furthermore, urea can significantly under-
mine the molecular hydrogen bond and hydrophobic interac-
tions of cellulose and chitin and then raise the critical micelle
concentration. It can also promote the solubility of polysaccha-
ride molecules and reduce the self-aggregation behavior in solu-
tion. Therefore, an alkali-urea solution can be used as a novel
WWW.MATERIALSVIEWS.COM 45175 (2 of 10)
green solvent for cellulose/chitin and is expected to be used in
some more demanding fields such as food and biomedical.29 In
a previous study,30 we synthesized a chitin-based acrylate super-
absorbent in a NaOH/urea solution, using a static solution
polymerization method without nitrogen protection. It could
absorb 2833 g of distilled water, 544 g of running water, and
88 g of artificial urine per gram dry polymer. However, it is not
clear whether the urea is involved in the polymerization reac-
tion or affects the resin’s performance, and there is a lack of rel-
evant research. Furthermore, chitin is insoluble in common
solvents, so it is difficult to evaluate the role of urea with chitin
as the raw material. In previous studies, we found that the addi-
tion of ethylene diamine tetraacetic acid (EDTA) and urea in
the polymerization process can increase the adsorption of cop-
per ions on the polymer with chitosan as the raw material and
acrylic acid as the grafting monomer. Narayanan and Dhamod-
haran31 also found that a new super water-absorbing material,
which is synthesized by the reaction between chitosan, EDTA,
and urea, exhibits a very high water uptake capacity compared
with chitosan, a chitosan–EDTA adduct, and a commercial dia-
per material. Nevertheless, it is also difficult to determine the
excellent water absorption performance that is provided by the
addition of urea, because all the raw materials themselves con-
tained nitrogen.
In this study, the one-pot multicomponent method was used to
synthesize an ecofriendly starch-based superabsorbent compos-
ite. Starch (without nitrogen in itself) was used as the grafted
skeleton, acrylic acid as the grafting monomer, urea as the
structure and function modifier, ammonium persulfate (APS) as
the initiator, and N,N0 -methylenebisacrylamide (MBA) as the
crosslinker. A homogeneous gel-like starch-g-poly(acrylic acid)
superabsorbent polymer (SAP) was successfully obtained, with
various potential applications. The structure, properties, and
synthesis conditions were also investigated.
EXPERIMENTAL
Materials
Corn starch, sweet potato starch, and potato starch (food grade,
Shandong Bio Sunkeen Co., Ltd., Zoucheng, PRC), glutinous
rice flour (food grade, Xiamen Taihe Trading Co., Ltd., Xiamen,
PRC), wheat flour (food grade, Nanjiecun Group, Henan, PRC)
were purchased from the supermarket in Chizhou city. Acrylic
acid monomer (AR), ammonium persulfate (AR), and N,N0 -
methylenebisacrylamide (CP) were supplied by Shanghai
Reagent Corp. (Shanghai, China) without additional treatment.
All other commercially available solvents and reagents were ana-
lytical grade and used directly without further purification.
Preparation of Superabsorbent Polymers
Superabsorbent polymers were prepared using the one-pot mul-
ticomponent method. The procedure for synthesizing the urea-
containing SAP (USAP) is described in detail as an example.
The graft copolymerization was performed in a 100 mL beaker
without stirring and nitrogen protection. First, 0.30 g of starch
was dispersed in 5.40 mL of water in a small beaker, and then
3.60 mL of NaOH solution (including 0.90 g NaOH) was added
dropwise and mixed with the starch emulsion. After the starch
was fully gelatinized, 2.40 mL of urea solution (including 0.60 g
J. APPL. POLYM. SCI. , DOI: 10.1002/APP.45175
ARTICLE WILEYONLINELIBRARY.COM/APP
urea) and 1.20 mL of APS solution (30 mg APS) were added
subsequently and stirred for 0.5 h at room temperature. Then
1.20 mL of MBA solution (6.0 mg MBA) and 10.80 mL of AA
solution (3.60 mL AA mixed with 7.20 mL H2O) were added
into the mixed solution with stirring and finally sealed with
plastic film and maintained at 65 8C for 5 h. After graft copoly-
merization, the reaction mixture was cooled to room tempera-
ture, and a hydrogel was obtained. The purification and
subsequent processing of the hydrogel were in accordance with
the method that we previously reported.30 The yield of SAPs
was calculated by the ratio of the total weight of the final prod-
ucts and the total weight of the nonaqueous raw materials in
percentage. The blank control samples marked as PAA (without
starch) and SAP (without urea) were prepared in a similar way.
Properties
The water absorbency (Qe) of the samples in distilled water
(Qd), running water (Qr), normal saline (Qs), and artificial
urine (Qu) were tested according to the same method we previ-
ously reported.30 After reaching swelling equilibrium, an 80-
mesh nylon screen was used as a filter to separate the residual
water and the fully swollen hydrogel. The water absorbency was
calculated by the ratio of the net weight of the swollen superab-
sorbent polymer and the initial weight of the dried superabsor-
bent polymer (g/g).
The total nitrogen content in the SAP sample was determined
by the Kjeldahl method. The SAP samples were immersed in
different concentrations of calcium chloride solution, and after
swelling equilibrium, the calcium content in the unabsorbed
water was determined by the EDTA titration method.
Characterization
The composite polymers were immersed in distilled water at
room temperature to segregate the water-soluble component.
Every 8 h the swollen hydrogel was separated by an 80-mesh
nylon screen and immersed in new distilled water again. After
soaking for 48 h, the purified hydrogel was dehydrated by abso-
lute ethyl alcohol, then dried under vacuum at 60 8C and used
for characterization.
The powder X-ray diffraction (XRD) profiles were carried out
with a JDX-10P3A diffractometer (JEOL, Tokyo, Japan) with
the diffraction angle (2u) ranging from 48 to 608. The Fourier
transform infrared (FTIR) spectra were recorded on an FTIR
spectrometer (Nicolet iS10, Thermo Fisher, Waltham, MA)
using KBr pellets, with a resolution of 4 cm21 from 4000 to
400 cm21. The thermal stability of samples (around 8 mg) was
determined on an HTG-1 thermogravimetric analyzer (TGA,
Beijing Scientific Instrument Factory, Beijing, China), with a
temperature range of 30–650 8C at a heating rate of 10 8C/min
under a dry air atmosphere.30 About 5 mg of SAP was heated to
a preset temperature in the TGA under dry air atmosphere. All
samples were heated at 10 8C/min and then cooled to room
temperature as soon as possible. The residue was milled with
KBr, and the FTIR spectra were captured immediately using the
iS10 FTIR spectrometer and the KBr disk technique.32
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Macroscopic and Scanning Electron Microscopy Analysis
A small piece of sample (about 0.03 g) was immersed in distilled
water to reach swollen equilibrium. After about 24 h, the sample
absorbed water, formed a good hydrogel, and was photographed
by a digital camera (IXUS 300HS, Canon, Tokyo, Japan). Then
5 mL of iodine solution was dropped into the hydrogel, and the
hydrogel was washed three times with water and photographed
again after being held for 5 h. Subsequently, it was immersed in
distilled water for about 20 h and was photographed after any
excess water was poured out. Finally, the hydrogel was dried in
air at room temperature (approximately 32 8C) for 5 days and
then photographed. The microstructures of the original starch
granule, dry SAP, and PAA samples were investigated with a
JSM-6700F field emission scanning electron microscope (SEM;
JEOL, Tokyo, Japan).30
RESULTS AND DISCUSSION
Preparation of Superabsorbent Polymers
Influence of Reaction Conditions. With the urea dosage, starch
amount, and concentration kept constant, the other reaction
conditions that may affect the water absorption capacity were
discussed. The variation regularity is similar to that in the tradi-
tional methods.11,13 The swelling capacity increased with
increasing initiator APS concentration. A higher swelling capac-
ity is achieved at an initiator content range of 6.67–10 wt %
with respect to starch. Subsequently, the swelling capacity
decreased and the water solubility increased, probably due to
the reduction of the molecular weight of the graft copolymer
caused by the excessive free radicals. The swelling capacity
decreased and the gel strength increased with increasing content
of the crosslinker MBA. An appropriate MBA content is 2.0 wt
% with respect to starch. The ratio of monomer AA to starch
was another very important variable: the swelling capacity
increased with increasing content of AA, and an appropriate
ratio is about 10-14:1 (volume to mass). Beyond the optimum,
the values of swelling capacity decreased gradually, probably
because the excessive monomer leads to an increase in the
homopolymers formed. As a consequence, the high molecular
weight polymer chain entanglement increased, as well as the
crosslinked density.
The PAA-based superabsorbent polymer is a typical ionic poly-
mer. In this work, only a very small part of NaOH was used to
gelatinize and dissolve the starch. Most of the NaOH was used
to adjust the neutralization degree of the monomer AA. The
purpose of neutralization is to increase the amount of hydro-
philic groups ACOONa in the polymers and increase the
osmotic driving force for water absorption, thereby increasing
the water absorption capacity. However, more excessive
ACOONa should increase the water solubility too. An appropri-
ate ratio of NaOH to starch is 2.67-3.67:1 (mass ratio); mean-
while the neutralization degree (ND) of AA is only about 32–
44%. The swelling capacity declined rapidly with a further
increase in the amount of NaOH, while the water solubility
increased gradually. This is lower than that of other reports in
the range of 50–85%.13 Such differences may be due to the
addition of urea during the synthesis process. It is known that
organic acids can react with urea.33 Therefore, a part of the
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Figure 1. Effect of urea content on the swelling capacity and N content of the
polymers: m (starch) 5 0.60 g, wt % (starch) 5 1.25%, V (AA) 5 5.40 mL, m
(NaOH) 5 1.20 g, m (APS) 5 40 mg, m (MBA) 5 10 mg, T 5 65 8C, time
5 5.5 h. [Color figure can be viewed at wileyonlinelibrary.com]
ACOOH groups are converted to ACOONH2 groups during
the polymerization process, which can also lead to an increase
in ND. However, ND is defined as the degree of neutralization
of acrylic acid by sodium hydroxide, so the contribution of urea
is not included in the calculation of ND in this paper.
APS is a typical thermally dissociated initiator, and the reaction
temperature mainly affects the decomposition of APS and the
generation efficiency of free radicals. There was very little prod-
uct at low reaction temperature, the yield increased with
increasing temperature, and the swelling capacity also increased
before the temperature reached 75 8C. Beyond 75 8C, the swell-
ing capacity declined rapidly and the water solubility increased
gradually. Furthermore, a hydrogel with a weaker gel strength is
formed when the reaction temperature is higher. An appropriate
temperature range is 65–75 8C.
The reaction time mainly affects the yield and gel strength after
absorbing water. It is conducive to forming a perfect three-
dimensional network structure, at a relatively low temperature
for a long time, thereby improving yield, water absorption
capacity, and gel strength. However, the crosslinked density will
be large when the reaction time is too long, leading to a rapid
decrease of the swelling capacity. Therefore an appropriate reac-
tion time range is 3–5 h.
Influence of the Amount of Urea. The influence of urea in the
polymers on the water absorbency and yield is shown in Figure
1. It can be seen that the urea dosage has a large impact on the
water absorption capacity of the polymers. The Qd increased
significantly with increasing urea dosage, while the Qr increased
slightly. Beyond the optimum dosage, the values of Qd and Qr
all decreased considerably. This is similar to the influence of
NaOH. Meanwhile, the N content also increased with increasing
urea dosage. This shows that the urea participated in the poly-
merization. With heating and the presence of water, one mole-
cule of urea can be hydrolyzed eventually to produce two
molecules of NH3. Then NH3 can neutralize the ACOOH
groups of acrylic acid and adjust the neutralization degree. The
Qd is higher than that of superabsorbent polymers without
WWW.MATERIALSVIEWS.COM 45175 (4 of 10)
Figure 2. Effect of the starch concentration on the swelling capacity and yield
of polymers: m (starch) 5 0.60 g, V (AA) 5 5.40 mL, m (NaOH) 5 1.20 g, m
(urea) 5 1.0 g, m (APS) 5 50 mg, m (MBA) 5 12 mg, T 5 65 8C, time 5 5.5 h.
[Color figure can be viewed at wileyonlinelibrary.com]
urea, and it may be interpreted that the collaborative absorbent
effect of the groups is superior to that of single ACOONH2,
ACOONa, or ACOOH groups.34 This is similar to the phe-
nomenon in which the Qe of the SAPs copolymerized with a
variety of hydrophilic monomers was better than that when
grafted by a single monomer.
The salting-in effect of urea can reduce the solvent aggregation
power of the solvent system, increase the critical micelle concen-
tration, and damage the hydrophobic interaction, which can
then reduce the aggregation tendency of the aggregator. Thus,
urea has been used successfully in dissolving the refractory
insoluble macromolecules such as chitin, cellulose, and polyani-
line, with the synergy of NaOH under low temperature.29,30 In
this work, the first aim of adding urea was to make the starch
molecule chains become more extensive in the solution. During
the reaction, the decomposition of urea produces NH3 mole-
cules and introduces them into the products, which can form
another hydrophilic group COONH2. Simultaneously, urea as a
pore-forming agent can make the porous structure for the
hydrogel.
Influence of Starch Concentration. As shown in Figure 2,
accompanying the increase of water added into the reaction sys-
tem, the concentration of starch and other reagents decreased,
and the yield of products decreased quickly. However, the water
absorbency of the polymer increased rapidly and reached a
maximum value when the starch concentration was around 0.9
wt % and then declined sharply. If the starch concentration is
low, although the starch molecular chain can be more stretch-
able, the concentrations of crosslinker, initiator, and monomer
are low due to the large amount of added water. The starch
molecule chains were difficult to put in contact with the initia-
tor, crosslinker, and monomer, so only a looser three-
dimensional network structure can be formed. Therefore,
although the water absorption capacity is high, the gel strength
was very weak. The viscosity of the system increased with
increasing starch concentration; apparently the kinetic probabil-
ity of a starch molecule being attacked by initiator, crosslinker,
and monomer increased greatly. The crosslink density and the
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Table I. Swelling Capacity of SAPs Synthesized under the Optimum Conditions
Sample Yield (%)
Corn starcha 99.0
b
Corn starch 90.3
Potato starchb 89.0
Sweet potato starchb 90.6
Wheat flourb 85.7
Polished glutinous rice powderb 85.0
PAAc 91.9
a
SAP synthesized under the optimum conditions without urea.
b
USAP synthesized under the optimum conditions.
c
PAA synthesized under the optimum conditions without starch and urea.
gel strength increased, while the water absorption capacity less-
ened considerably. However, when continuing to elevate the
starch concentration, the viscosity becomes too high, and as a
result the movements of the starch molecule chains, the free
radicals, and the monomers are hindered. The operation is diffi-
cult to control. The products are more heterogeneous, and the
water absorbency of the polymer is low.
Optimal Synthesis Conditions. Based on our previous work, a
L18(38) orthogonal experiment design was applied to investigate
the effects of different reaction conditions on the water absor-
bency, yield, and gel strength. The optimal synthesis conditions
were obtained: m (starch) 5 0.60 g, wt % (starch) 5 1.20%, V
(H2O) 5 39.20 mL, V (AA) 5 7.40 mL, m (NaOH) 5 2.0 g, m
(urea) 5 0.40 g, m (APS) 5 50 mg, m (MBA) 5 12 mg, T 5 65 8C,
and time 5 5 h. The swelling capacities of SAPs synthesized
under the optimum conditions using the one-pot multicompo-
nent method are shown in Table I. The swelling capacities of
the SAPs synthesized with several different kinds of starches all
reached considerable values, although they seemed slightly less
than the values of PAA. This does not prevent the one-pot mul-
ticomponent method from becoming a rapid and universally
applicable method for synthesizing starch-based superabsorbent
polymers.
Many literature reports can be found on superabsorbent pro-
duction based on different sources of starches.13 The composi-
tions of amylose, amylopectin, and functional groups within the
starch molecules were also different, so the water absorption
capacities were significantly different. Corn starch is the most
abundant commercial plant starch on earth. Corn starch and its
derivatives are also the most widely used materials for develop-
ing starch-based SAPs.27 Potato starch is the second-most abun-
dant commercial plant starch after corn starch. The starch
granules are bigger than in most commercial starch products
and have a stronger swelling power and are more easily dis-
solved. Thus, the starch molecular chains are more stretched.
The reaction with acrylic acid is more thorough. In addition,
potato starch contains more hydrophilic phosphate groups in its
molecular structure. The swelling capacity of potato starch
based SAPs is the best.
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Water swelling capacity Qe (g/g)
Qd Qr Qs Qu
2546 6 180 518 6 50 95 6 5 90 6 3
2704 6 22 561 6 39 100 6 5 96 6 4
2739 6 116 570 6 14 99 6 6 106 6 3
2649 6 128 559 6 65 104 6 7 103 6 3
2559 6 151 504 6 10 94 6 5 91 6 3
2643 6 147 491 6 9 93 6 1 98 6 2
2927 6 71 564 6 29 110 6 4 99 6 3
The average particle size of the sweet potato starch granules is
smaller than that of the corn and potato starch, and the swell-
ing power and solubility are slightly lower. Therefore, under the
optimum reaction conditions at a temperature of 65 8C, the
starch molecular chain is difficult to sufficiently extend, result-
ing in slightly lower water absorption capacity than that pre-
pared from corn and potato starch. A similar observation was
reported by Liu et al.17 on the water swelling capacity of starch-
based SAPs produced from potato and sweet potato starch.
They found that polymers made from both kinds of starch
showed similar gel strength but with significantly different water
absorption capacity. The difference is significantly greater than
that between the two SAPs prepared with the method used in
this work. Furthermore, the amylose content in sweet potato
starch is lower than in potato and corn starch. This also leads
to a decrease in the swelling capacity.27 Polished glutinous rice
powder, in addition to containing more amylopectin content,
also contains some protein and fat. So both the swelling capac-
ity and yield were lower than for SAPs made from corn or
potato starch. There is more gluten in wheat flour, resulting in
lower swelling capacity and yield than when using corn or
potato starch. Furthermore, for comparison purposes, the water
absorption capacities of various biomass-based SAPs reported in
the literature are presented in Table II. The water absorption
capacity of the sample in this work is greater than that of most
similar samples reported in the literature. The main reason may
be that the crosslink density of the products is different.
Characterization
FTIR Analysis. FTIR analysis was employed to investigate the
change of functional groups between the SAPs, PAA, and native
starch. The FTIR spectra are given in Figure 3. It can be seen
that the spectrum of the original starch exhibited a pattern sim-
ilar to that in previously reported results.6,15,27 The typical IR
spectra of starch and PAA were observed, and the attribution of
the primarily absorption peaks has been discussed in detail in
previous literature, and some of the characteristic absorption
peaks are also presented in Figure 3.
The FTIR spectrum of SAP and USAP exhibited a similar pat-
tern. It can be seen that there is no significant difference in the
molecular structure between the SAPs synthesized with urea and
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ARTICLE WILEYONLINELIBRARY.COM/APP

Table II. Water Absorption Capacities of Various Biomass-Based Superabsorbent Polymers

Qe (g/g)
Sample Qd Qs Reference
Solution polymerization method
6,15,27
Corn starch based SAPs 190–1800 —
16,20
Wheat St-g-PAA/PAM 150–166 —
17
Potato St-g-PAA 1180 86
20
Amaranthus St-g-PAA/PAM 155 —
17
Sweet potato St-g-PAA 230 65
35
Cassava St-g-PAM 605 —
7
Cotton stalk cellulose based SAPs 1125 126
7
Flax yarn waste cellulose based SAPs 875 90
9
Chicken feather Pr-g-PAA/PVA 714 70
31
CTS-EDTA-urea 570 —
1
Potato St-g-PAA/attapulgite 1077 61
35
Cassava St-g-PAM/clay 730 —
Radiation method
36
Cassava St-g-PAA/PAM 1142 —
37
Cassava St-g-PAM-co-(maleic acid) 2653 94
19
Sago St-g-PAA 4192 —
One-pot method
38
Corn St-PAM-urea 80–253 —
Corn St-g-PAA/urea 2704 100 This work

without urea. Compared to the IR spectrum of PAA, similar
absorption peaks appeared in the regions of 3500–2800 cm21
and 1600–1200 cm21 and around 1710 cm21. Also, in compari-
son with the IR spectrum of native starch, similar absorption
peaks also appeared in the region of 1200–900 cm21, which are
the characteristic peaks in the starch structure. Before being
used to obtain the FTIR spectra, all of the modified samples
were purified to remove the homopolymers and unreacted
agent. So, from the above FTIR information, it can be con-
cluded that the PAA chains were successfully grafted onto the
starch skeleton during the polymerization. Besides, the absorp-
tion peaks in the fingerprint region at 930 cm21 (w), 856 cm21
(w), and 577 cm21 (m) are attributed to the CAOH bending,
CAOAC symmetrical stretching, and the skeletal vibration of
the pyranose ring, respectively. They became smaller after poly-
merization, which indicated that graft copolymerization
occurred between the acrylic acid monomer and the molecular
starch.1
XRD Patterns. X-ray diffraction patterns of the original corn
starch, the SAPs, and PAA are illustrated in Figure 4. Starch
granules are semicrystalline in nature. The XRD pattern of corn
starch consists of two parts, sharp diffraction peaks and diffuse
diffraction peaks, which is a typical polycrystalline diffraction
curve. The single diffraction peak at 15.178, 23.158 and the dual
peaks at 17.0–18.1 8 were observed in the 2u range of 4–608 and
were indexd as (220), (121), (301), and (020), respectively. No
diffraction peak appears around 2u 5 5.6 8, which is characteris-
tic of a B-type pattern. This suggests that the native corn starch
is an A-type crystal structure.20 The PAA, SAP, and USAP
exhibited highly similar XRD patterns. Compared with the pat-
tern of native starch, the sharp crystalline diffraction peaks dis-
appeared, and only a broad, diffuse diffraction peak was located
at approximately 2u 5 21.78, indicating that the crystal structure
was destroyed during the graft polymerization. It can be con-
cluded that the one-step method for the graft copolymerization
reaction can be carried out thoroughly. The hydrogen bonding
ability of starch was weakened after PAA chains were grafted
onto the starch backbone.
Thermal Stability. The thermal stability was examined by ther-
mogravimetric analysis and FTIR. The TG, DTG, and DTA
curves of native starch, SAPs, and PAA are given and compared
in Figure 5. The maximum decomposition speed can be con-
firmed from the DTG curves. The thermal decomposition pro-
cess can be determined from the TG curves with the assistance
of the DTA curves. The TG/DTG curve for starch is similar to
that reported in previous literature,1,15 with a total weight loss
of 97.7%. The thermal behavior of starch can be divided into
three stages (Table III). The first stage is attributed to the
vaporization of free water and bound water. A definite weight
loss was observed in the second stage with a maximum decom-
position rate at 297 8C, implying depolymerization and inter-
ruption of the starch molecular chains. The sample weight
decreased very slowly in the third stage, which is attributed to
the charring and complete degradation of the glucose residues.
In the DTA curve, the exothermic peak around 358 8C is
ascribed to the melting peak with thermal decomposition.

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Figure 3. FTIR spectra of native corn starch (St), superabsorbent polymers

(SAP and USAP), and pure poly(acrylic acid) (PAA). [Color figure can be
Figure 4. XRD patterns of PAA, SAPs, and original corn starch. [Color
viewed at wileyonlinelibrary.com]
figure can be viewed at wileyonlinelibrary.com]

The thermal properties of UPAA and PAA were very similar, as

In order to better understand the decomposition of USAP, the
well as of the USAP and SAP; the sample weight declined slowly
FTIR spectra of the residues obtained from heating USAP to a
in the full range. The weight losses are listed in Table III. In the
certain temperature are given in Figure 6. There is no significant
case of PAA and UPAA, the addition of urea resulted in a stron-
difference between the original USAP and that heated to 190 8C.
ger water absorption capacity. However, there was no significant
With an increase in temperature to 280 8C, the peak at
effect on the thermal stability of the pure poly(acrylic acid)
1713 cm21(s) ascribed to C@O stretching weakened, and then
chains. After copolymerization with starch, the thermal proper-
disappeared when the temperature was increased to 375 8C.
ties were similar to that of PAA, but with some differences in
With a further increase of the temperature to 450 8C, new peaks
details. The weight loss of SAP is minor compared to that of
reappeared at 1732 cm21(w), 1660 cm21(m), and 839 cm21(m).
USAP in the first stage, suggesting more free water is absorbed
The peak at 1453 cm21(s) can be assigned to the COO21
by USAP than by SAP. Both are also lower than that of UPAA
stretching of carbonate, which became stronger when the tem-
and PAA, implying that the introduction of the starch molecu-
perature was increased to 515 8C, due to the formation of
lar chain attenuates the affinity between PAA and water, which
sodium carbonate. From the above FTIR information, it can be
is consistent with the water absorption results shown in Table I.
concluded that the thermal decomposition of USAP can be
In the DTA curves, the exothermic peaks around 330 8C and
divided into four stages (Table III). The first stage is assigned to
386 8C are ascribed to the oxidation and thermal decomposition
the loss of free and bound water, and the second stage corre-
peaks, and the peaks around 500 8C may be due to the forma-
sponds to the decarboxylation of PAA and the scission of mac-
tion of carbonate. The sodium content of USAP calculated
romolecular chains. The third stage is due to the decomposition
from the residual mass is roughly consistent with that calculated
(thermal and oxidative) and charring of the propylene and
by the amount of NaOH added before the reaction. The total
pyranose residues, and the final stage is attributed to vaporiza-
weight loss of USAP is less than that of PAA, UPAA, and SAP,
tion, elimination of volatile products, and the formation of
implying that urea was not only involved in the polymerization
carbonate.
reaction but also improved the thermal stability of the USAP.
This is probably because the nitrogen was doped into the car- Morphological and Absorption Analysis. The SEM micro-
bonate under a higher pyrolysis process. graphs of corn starch, USAP, and PAA are shown in Figure 7.

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Figure 5. TG, DTG, and DTA curves of original corn starch, SAPs, and
Figure 6. FTIR spectra of USAP before and after degradation. [Color
PAAs. [Color figure can be viewed at wileyonlinelibrary.com]
figure can be viewed at wileyonlinelibrary.com]

As can be seen, there are obvious discrepancies between their

color of PAA is orange, whereas that of USAP is navy blue,
surface structures. The corn starch appears to have a smooth
which is consistent with the discoloration phenomenon of
and dense structure; in comparison, the surface structure of
starch in an iodine solution. It can be concluded that the graft
PAA is coarse and loose. After polymerization, the surface struc-
polymerization did not destroy the whole starch molecular
ture of USAP becomes tight and porous, and this is obviously
chain. A part of the double-helix structure of starch still exists
different from that of raw starch and PAA, which is further evi-
in the USAP structure, which means that the USAP resin may
dence supporting the occurrence of graft polymerization
have certain adsorption properties. There is no Ca21 remaining
between PAA and corn starch.6,15
after immersing the USAP in running water. When the USAP
There is a substantial difference between the appearance of was immersed in a 0.06 mg mL21 Ca21 solution, the swelling
USAP and PAA hydrogel immersed in an iodine solution. The capacity is 506 6 5 g/g and the demineralized rate is 100%.

Table III. Weight Loss of Starch, SAP, and PAA

Weight loss (%)

First stage Second stage Third stage Fourth stage
Sample 100 8C 100–200 8C 200–350 8C 350–450 8C 450–550 8C Total Residue weight (%) at 650 8C
Starch 4.8 0.4 71.9 20.6 (2550 8C) 97.7 2.3
PAA 4.4 5.6 29.1 25.2 11.8 (2507 8C) 76.1 20.9
UPAA 4.5 8.0 29.4 27.9 9.3 (2507 8C) 78.1 20.1
SAP 2.1 4.9 32.8 23.9 (2476 8C) 13.4 77.1 21.2
USAP 3.3 4.8 30.5 19.8 (2476 8C) 13.4 70.8 28.7

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Figure 7. SEM micrographs of corn starch, USAP, PAA, and photographs of iodine-stained USAP and PAA. [Color figure can be viewed at
wileyonlinelibrary.com]
When the USAP was immersed in 0.2 and 1.0 mg mL21 Ca21
solutions, the swelling capacity is 100 6 4 and 17 6 1 g/g, the
Ca21 adsorption capacity is 73.9 6 1.8 and 157.0 6 6.0 mg/g,
and the demineralized rate is 46.2 6 1.2 and 19.6 6 0.7%,
respectively. This implies that the USAP has good adsorption
properties for mineral ions. The main reasons for adsorption
are the ion exchange and chelation between the mineral ions
and the carboxyl and amide groups, which will be investigated
in more detail in future studies.
CONCLUSIONS
In this study, starch is used as the grafted backbone, acrylic acid
as the grafting monomer, ammonium persulfate as initiator,
N,N0 -methylenebisacrylamide as the crosslinker, and urea as the
performance regulator. A homogeneous gel-like starch-g-poly(a-
crylic acid) superabsorbent polymer with urea was successfully
obtained using the one-step polymerization method. The starch
was dissolved in a NaOH solution without further gelatinizing
processing, and acrylic acid was directly used without prior
neutralization. In fact, all of the reagents, AA, APS, MBA, and
urea, can be mixed directly or added into the starch alkaline
WWW.MATERIALSVIEWS.COM 45175 (9 of 10)
solution at the same time, which can obviously simplify the
synthesis procedure and reduce water consumption as well as
lessen waste emission. Urea can significantly increase the water
absorption of the SAP. The sample that was synthesized under
the optimal conditions can absorb water 2704 and 100 times its
own dry weight in distilled water and 0.9% NaCl solution,
respectively. The FTIR results revealed that PAA chains were
successfully grafted onto the starch backbone. The XRD and
SEM results also provide indirect evidence of the occurrence of
graft polymerization between PAA and starch. The thermal anal-
ysis and nitrogen content results proved that urea was involved
in the polymerization reaction. The iodine-staining results show
that the grafting reaction does not completely destroy the
molecular structure of the starch, implying that the polymers
may have a good adsorption property.
ACKNOWLEDGMENTS
The authors are grateful to the support of the National Natural
Science Foundation of China (No. 51403024, 21271035) and the
Natural Science Foundation of Anhui Provincial Education
Department (No. KJ2015A282, KJ2016A512).
J. APPL. POLYM. SCI. , DOI: 10.1002/APP.45175
ARTICLE WILEYONLINELIBRARY.COM/APP
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J. APPL. POLYM. SCI. , DOI: 10.1002/APP.45175