Bioresource Technology 102 (2011) 28532858

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Synthesis and characterization of a novel super-absorbent based on wheat straw

Zuohao Ma, Qian Li , Qinyan Yue, Baoyu Gao, Xing Xu, Qianqian Zhong
Shandong Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Shandong University, 250100 Jinan, PR China

a r t i c l e

i n f o

Article history:
Received 6 August 2010
Received in revised form 15 October 2010
Accepted 15 October 2010
Available online 20 October 2010
Keywords:
Wheat straw
Super-absorbent polymer
Water absorbency
Graft copolymerization

a b s t r a c t
In order to develop an eco-friendly polymer, a novel super-absorbent polymer was prepared by graft
copolymerization of acrylic acid (AA), acrylic amide (AM) and dimethyl diallyl ammonium chloride
(DMDAAC) onto the pretreatment wheat straw (PTWS). The molecular structure of the super-absorbent
was conrmed by FTIR. The factors that can inuence absorbencies of the super-absorbent resin (SAR)
were investigated, such as weight ratio between the monomers, the ratio of PTWS to monomers, the
amount of initiator and cross-linker, temperature reaction time and neutralization degree of AA. The
SAR has the water absorbency of 133.76 g/g in distilled water and 33.83 g/g in 0.9 wt.% NaCl solution.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
Super-absorbent resin (SAR) is a three dimensional cross-linked
resin gel which is formed by the hydrophilic group and the organic
groups of carbon chain (Wang and Liu, 2006). SAR is a new functional polymer material, which can absorb a large amount of water,
where the weight can reach several hundred times its own weight
and has excellent water retention even under some pressure. It has
exhibited potential for application in many elds such as agriculture, hygienic products, waste-water treatment, drug-delivery
and coal dewatering (Chu et al., 2006; Kamat and Malkani, 2003;
Yi and Zhang, 2008; Sadeghi and Hosseinzadeh, 2008; Ende et al.,
1995).
Many kinds of materials have been used for preparing superabsorbents. And most of the traditional water absorbing materials
are acrylic acid and acrylamide-based products. They have poor
degradability. About 90% of super-absorbents are used in disposable products and most of them are disposed of by landlls or by
incineration (Kiatkamjornwong et al., 2002). And there will be an
environmental problem with super-absorbent polymers (Zhang
et al., 2007, 2006). Meanwhile it has low absorption rate under
the high concentration of electrolyte, undesirable water-keeping
capacity and high cost (Wang and Liu, 2004).
In order to solve those problems, considerable attention has
been paid to the naturally available resources such as polysaccharides and inorganic clay mineral (Ray and Bousmina, 2005; Li et al.,
2007). It has good commercial and environmental value with the

Corresponding author. Tel.: +86 531 88365258; fax: +86 531 88364832.
E-mail address: qianli@sdu.edu.cn (Q. Li).
0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.10.072

advantages of low cost, renewable and biodegradable polysaccharides for deriving super-absorbents (Pourjavadi and Mahdavinia,
2006; Yoshimura et al., 2005). Recently, a series of new superabsorbents characterized by eco-friendliness and biodegradability
were made from some natural materials, such as starch, cellulose,
chitosan (Lanthong et al., 2006; Peng et al., 2008; Farag and
Al-Afaleq, 2002; Wu et al., 2008), which were used to react through
radical graft polymerization with vinyl monomers and crosslinking agent.
Wheat straw, as a by-product of grain crops, is an important
biological resource in the crop production system (Talebnia et al.,
2010). It contains a high content of natural cellulose, hemicellulose
and lignin. However, this resource has not been properly used; except for a limited utilization as pulp, feed and other purposes,
wheat straw is mostly incinerated. It is not only a huge waste of
natural resource, but also a serious pollution to the environment
(Dunford and Edwards, 2010). Wheat straw can be modied
through chemical method and used as skeletal material, on which
some monomers such as AA and AM can graft so as to form superabsorbent composite (Rmond et al., 2010; Davies et al., 2004; Kim
et al., 2002).
In recently years, progress has been made in this eld. A singleion SAR was produced through the copolymerization of wheat
straw and acrylic acid (Sun et al., 2007). Wheat straw was modied
by chemical method to form cellulose derivatives such as carboxymethyl cellulose, which was used to graft with some monomers to
prepare the super-absorbent composite (Bai et al., 2003). But there
are few reports on the preparation of an amphoteric super-absorbent polymer, which have better water absorbency than the single-ion SAR by using wheat straw directly. In our study, a new,
eco-friendly and amphoteric SAR was investigated. It was based

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Z. Ma et al. / Bioresource Technology 102 (2011) 28532858

on pretreatment wheat straw (PTWS), acrylic acid (AA), acrylic

amide (AM) and dimethyl diallyl ammonium chloride (DMDAAC),
with potassium persulfate (K2S2O8), cerium ammonium nitrate
((NH4)2Ce(NO3)6) and Na2SO3 as initiator and N,N0 -methylenebisacrylamide (MBA) as cross-linker. In order to nd the optimum
synthesis conditions, the properties and synthesis conditions of
the SAR were investigated. The synthetic process of the superabsorbent is eco-friend mainly. All the raw materials added are
transformed into product. And no discharge of waste or pollutant
is produced to the environment. The product does not produce secondary pollution during use.
In our study, the basic skeleton of the synthetic product is natural cellulose which can be used as organic matter of soil. Copolymers of acrylic acid and acrylamide have been widely used for soil
improvement. Dimethyl diallyl ammonium chloride copolymer is
non-toxic and used as polyquaternium occulant, which is widely
used in water treatment, food processing and fermentation industries. They are prone to be treated in soil by natural method. When
the polymer with the cellulose skeleton is applied to unit area of
soil, it will bring less organic into the soil than the soil improved
agent such as the polyacrylic acid and polyacrylamide. Meanwhile
the polymer with the cellulose skeleton would be easily decomposed in the soil. For these reasons, the new SRA could be decomposed in soil under normal conditions especially through
ecological ways.

2. Experiment
2.1. Materials
Wheat straw was obtained from Liaocheng, Shandong Province
(China). Acyclic acid (AA, A.R., purchased from Tianjin China), acrylic amide (AM, C.R.), dimethyl diallyl ammonium chloride
(DMDAAC, C.R.) and N,N0 -methylenebisacrylamide (MBA, A.R.)
were prepared by dissolving in distilled water. Other agents used
were of analytical grade and all solutions were prepared with distilled water.
2.2. Pretreatment of wheat straw
The wheat straws were cut, washed and dried in a 105 C drying
oven for 12 h. The dried wheat straw were smashed and sifted.
Then it was weighed and dipped in a 500 ml beaker with 10%
ammonia at the mass ratio of 1:12 for 48 h, and the mixture was
ltered and washed. After that, the ltered residue was transferred
into a new beaker with 1 mol/l nitrate at the mass ratio of 1:12,
and heated at 100 C for 45 min. Finally, the mixture was ltered,
washed by distilled water and then dried at 105 C for 24 h to obtain the pretreated wheat straw (PTWS).
2.3. Preparation of the wheat-straw-based super-absorbent
composites
The PTWS (1.0 g) was added into a three-necked ash, which
was equipped with a stirring apparatus. Then various amount of
K2S2O8 and (NH4)2Ce(NO3)6 dispersed in moderate amount of
deionized water were added into the ash to initiate the graft polymerization. The solution was heated by a water bathe for 15 min,
in which the water was kept at 50 C. A certain amount of Na2SO3,
AA after neutralization, AM and DMDAAC were added. Then, the
MBA as the cross-linker was added 1 h later. Finally, after 4 h reaction, the resulting product was dried to a constant at 70 C. Moreover the SAR was milled, sifted through a 20-mesh sieve to prepare
samples.

2.4. Water absorbency measurement

To determine the water absorption capability, 0.50 g of the sample was immersed in distilled water and saline solution at room
temperature to swell, respectively. Then the swollen sample was
taken out and the excess water was removed by a 100-mesh gauze.
The weight of the swollen samples was measured. The water
absorbency (Q, g/g) was calculated by

Q M 2  M 1 =M 1

where, M1 and M2 are the weights of the dry and the swollen sample
(g), respectively.
2.5. FTIR spectroscopy
FTIR spectrum was obtained on a NEXUS-470 series FTIR spectrometer (Thermo nicolet, NEXUS). The samples were taken into
KBr pellets.
3. Results and discussion
3.1. Effects of the synthesis conditions on the water absorption
properties of the super-absorbent polymer
The super-absorbent polymers prepared under different synthesis conditions have different water absorbencies due to the different structures (Liang and Liu, 2006). So the effects of different
synthesis conditions on the water absorbencies of the super-absorbent polymers were investigated.
3.1.1. Effect of the ratios of the monomers and PTWS
The effects of different amounts of three kinds of monomers
(AA, AM, DMDAAC) and PTWS on the water absorbencies of the
SAR were studied and the results were shown in Table 1.
The effect of weight ratio of AA to monomers (ranging from 2:7
to 6:7) on the absorbencies was investigated. As shown in Table 1,
the water absorbency increased continuously with the increase of
the weight ratio of AA to monomers until the maximum water
absorbency was reached, which was 118.65 g/g in distilled water
and 33.88 g/g in 0.9 wt.% NaCl solution, respectively. And the optimal weight ratio of AA to monomers was 4:7. It can be explained as
follows: as the weight ratio of AA to monomers increased, more
and more hydrophilic groups such as COO and COOH were
grafted onto the PTWS, which could enhance the water absorption
capacity of the SAR. In addition, more ions were generated in the
polymeric network and therefore the osmotic pressure between
the polymeric network and external solution increased (Liu et al.,
2009). When the ratio was greater than 4:7, the water absorbency
decreased, for the reason that the polymeric network became
much closer as the ratio of AA to monomers became lager which
was not conducive to absorbencies.
The effects of weight ratio of AM and DMDAAC to monomers on
the absorbencies were studied, as shown in Table 1. It can be seen
that the water absorbency increased with the ratio of AM to monomers increasing, and reached the maximum, then dropped. The
same tendency was also found in the effect of DMDAAC. The biggest water absorbency was obtained at the ratio of 2:7 for AM to
monomers and 1:7 for DMDAAC to monomers, respectively. The
reasons were similar: when the monomer increased, the grafting
rate increased and the branch chain grafted in cellulose became
long, which was conducive to the formation of the ideal network
structure of resin and as a result increased the water absorbency.
Furthermore, the effect of weight ratio of PTWS to monomers
on the water absorbency was also investigated (Table 1). As the
weight ratio increased, the water absorbency increased very

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Z. Ma et al. / Bioresource Technology 102 (2011) 28532858

Table 1
Effects of the mass ratios of the monomers and the PTWS on water absorption capacities (Mm stands for the mass of the monomers).
M (DMDAAC)/Mm

M (AM)/Mm

M (AA)/Mm

M (PTWS)/Mm

Qd in the distilled water (g/g)

Qs in the saline solution (g/g)

0:7
0.5:7
1:7
2:7
3:7
1:7

2:7

4:7

1:7

4:7

1:7

1:7

0.5:7
1:7
2:7
3:7
4:7
2:7

1:7

1:7

2:7

2:7
3:7
4:7
5:7
6:7
4:7

83.23
91.78
118.65
42.79
43.48
97.21
110.57
118.65
79.24
74.09
70.12
91.63
118.65
82.34
112.14
131.25
133.76
123.19
117.91
67.58

25.56
27.78
33.89
18.49
17.38
35.48
32.63
33.88
24.97
21.05
23.12
25.45
33.88
25.13
23.47
32.49
33.38
33.67
28.22
18.54

0.3:7
0.5:7
1:7
1.5:7
2:7

slowly. The change of the water absorbency was almost at, and
when the ratio was higher than 1:7, it decreased quickly. It can
be explained that when the ratio was small, the skeleton of the cellulose was loose and it was easy for more monomers to be grafted.
When the ratio was higher than the saturation, the polymeric network became closer as more and more monomers grafted to the
cellulose. Thus the water absorbency dropped.
The content of PTWS (the biological content) to prepare the
super-absorbent resin was 1/8. The 1/8 is only the mass ratio,
which seems that the ratio of PTWS is small compared with the ratio of organic. But with the reason of small density, the wheat
straw has a larger volume ratio or molar ratio than the organic.
And the form of the product we gotten is similar with wheat straw.
In order to nd the best ratio of AA, AM, DMDAC and PTWS,
orthogonal experiment of four factors and three levels was conducted. A stands for the mass of PTWS , which has three levels
of 0.5, 1, and 1.5 g. B, C and D standing for the mass of
DMDAAC, AM and AA, respectively. According to the orthogonal array of L9(3)4, the following experiments were performed (Table 2),
and the result of range analysis was shown in Table 3.
Table 2 showed that the best ratio of materials to prepare superabsorbent resin was m(PTWS):m(AA):m(AM):m(DMDAAC) =
1:4:2:1. The result of the range analysis indicated that the order
of the inuence of each factor on the water absorbency was
D > B > C > A in distilled water and A > C > D > B in 0.9 wt.% NaCl
solution, respectively. In the distilled water, AA is the most important factor, DMDAAC followed, then AM and PTWS are the last. In
the synthetic reaction, hydrophilic groups such as COO and
COOH are grafted in the cellulose skeleton from AA, which can

Table 2
The orthogonal experiment of PTWS, AA, AM and DMDAAC (A: the weight of PTWS; B:
the weight of DMDAAC; C: the weight of AM; D: the weight of AA. Qd: the water
absorbency in the distilled water; Qs: the water absorbency in saline solution).
Sample no.

A/g

B/g

C/g

D/g

Qd (g/g)

Qs (g/g)

1
2
3
4
5
6
7
8
9

0.5
0.5
0.5
1
1
1
1.5
1.5
1.5

1
2
4
1
2
4
1
2
4

1
2
4
2
4
1
4
1
2

1
2
4
4
1
2
2
4
1

48.24
77.93
71.98
118.00
70.72
37.17
67.17
85.48
17.66

14.23
25.76
26.24
33.55
23.27
16.64
17.46
14.65
11.46

Table 3
Analysis of orthogonal L9(3)4 experiment (A: the weight of PTWS; B: the weight of
DMDAAC; C: the weight of AM; D: the weight of AA).
A

k1a
k2
k3
Rb
0
k1 c

66.05
75.30
56.98
18.32
22.08

77.80
78.04
45.57
32.47
21.75

56.96
71.20
70.17
14.24
15.17

45.54
60.97
91.82
46.28
16.32

k2

24.49

21.23

24.65

19.95

14.52

18.11

22.32

24.81

9.97

3.64

9.48

8.49

k3
R0 d
a
b
c
d

P
k1 = ( the water absorbency in the distilled water of single-factor)/3.
R1 = max K1  min K1.
P
0
k1 = ( the water absorbency in saline solution of single-factor)/3.
0
R1 = max K01  min K01 .

greatly improve the water absorbency of SAR. This factor has the
larger effect than other factors. When DMDAAC is grafted in the
polymer, NH
4 is connected to the skeleton. It increases moving ions
and the increasing hydrophilic can improve the water absorbency.
So the effect of DMDAAC on water absorbency is greater than AM
and PTWS. But in the 0.9 wt.% NaCl solution, the condition is different. AM is the nonionic hydrophilic monomer. Nonionic hydrophilic
groups CONH2 have a synergy with the anionic hydrophilic groups
COONa+, weakened the common ion effect and salt effect in the
bibulous process, so it can greatly improve the water absorbency
in the NaCl solution. But the AA and DMDAAC have the common effect and salt effect in the NaCl solution, which decrease the water
absorbency. So in the 0.9 wt.% NaCl solution the effect of PTWS
and AM are the most important effect.

3.1.2. Effect of the initiator content

The persulfate (K2S2O8), cerium ammonium nitrate ((NH4)2Ce(NO3)6) and Na2SO3 were used as the combined oxidationreduction system. The best mass ratio between them was m(K2S2O8):
m(Na2SO3) = 3:1 and m((NH4)2Ce(NO3)6):m(K2S2O8) = 1:5 (Guo
et al., 2006). The effects of the amount of initiator on the water
absorbency of the prepared polymers were studied with various
ratios of K2S2O8, which was represented as the amount of the initiator to the monomer. The result was shown in Table 4.
It indicated that the maximum absorbency was obtained at
1 wt.% of K2S2O8, which was 72.41 g/g in distilled water and

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Z. Ma et al. / Bioresource Technology 102 (2011) 28532858

Table 4
Effects of initiator, MBA, AA neutralization, temperature and time on the absorbencies.
Various factors in synthesis

The water absorbency in distilled water (g/g)

The water absorbency in 0.9 wt.% NaCl solution (g/g)

Effect of initiator to monomer ratio on absorbencies (m(AA):m(AM):m(DMDAAC):m(PTWS) = 4:2:1:1; the ratio of MBA to monomer = 0.6%; neutralization degree of
AA = 85%; temperature = 50 C; time = 5 h)
The ratio of K2S2O8 to monomers

0.6%
0.8%
1.0%
1.2%
1.4%

59.37
45.81
72.41
70.00
67.79

21.50
15.34
27.64
23.81
26.92

Effect of the amount of MBA on the absorbencies (m(AA):m(AM):m(DMDAAC):m(PTWS) = 4:2:1:1; the ratio of K2S2O8 to monomer = 1.0%; neutralization degree of
AA = 85%; temperature = 50 C; time = 5 h)
The weight ratio of MBA to monomers

0.10%
0.20%
0.40%
0.60%
0.80%
1.00%

90.72
96.68
70.44
72.41
68.44
58.16

26.75
29.97
27.62
27.64
21.25
21.54

Effect of AA neutralization on the absorbencies (m(AA):m(AM):m(DMDAAC):m(PTWS) = 4:2:1:1; the ratio of K2S2O8 to monomer = 1.0%; the ratio of MBA to
monomer = 0.6%; temperature = 50 C; time = 5 h)
Neutralization degree of AA

45%
60%
75%
85%
95%

35.6
50.13
57.76
70.15
69.60

15.93
17.78
19.47
27.64
22.34

Effect of temperature on the absorbencies (m(AA):m(AM):m(DMDAAC):m(PTWS) = 4:2:1:1; the ratio of K2S2O8 to monomer = 1.0%; the ratio of MBA to monomer = 0.6%;
neutralization degree of AA = 85%; time = 5 h)
Temperature (C)

30
40
50
60
70

59.32
69.72
72.51
54.14
48.15

21.15
22.49
27.64
21.88
21.25

Effect of time on the absorbencies (m(AA):m(AM):m(DMDAAC):m(PTWS) = 4:2:1:1; the ratio of K2S2O8 to monomer = 1.0%; the ratio of MBA to monomer = 0.6%;
neutralization degree of AA = 85%; temperature = 5 h)
Time (h)

2
3
4
5
6
7

68.44
69.40
72.31
72.51
44.76
55.60

27.64 in 0.9 wt.% NaCl solution, respectively. And the water absorbency increased totally with the increasing mass of K2S2O8. When
the amount of K2S2O8 was higher than the optimum point, the
change of the water absorbency became gentle and the water
absorbency decreased slowly with the increase of the amount of
K2S2O8. The cause was related to the relationship between average
chain length and concentration of the initiator in the polymerization (Zhang et al., 2009). More graft polymerization that occurred
between the monomers and the PTWS led to the formation of
more stable network structures, which was helpful to the increase
of the water absorbency. When the concentration of the initiator
was too high, there was a strong reaction with the cellulose
molecular, which resulted in the decrease of the main chain
length. Consequently, the water absorbency of the polymer
dropped.
3.1.3. Effect of cross-linker content
The effect of the amount of N,N0 -methylenebisacrylamide
(MBA), which was used as the cross-linker in the polymerization,
was studied and the result was shown in Table 4. When the ratio
of MBA to monomer was lower than 0.20%, the water absorbency
increased with the rising ratio; however it began to decrease with
the increasing ratio when it was higher than 0.20%. So the best dosage was at the ratio of 0.20%, where the maximal absorbency was
achieved (96.68 g/g in distilled water and 29.97 g/g in wt.% NaCl
solution).

20.89
26.23
21.37
27.64
20.11
19.90

According to Floy theory, increasing cross-linker could increase

the nodes of network and the cross-linker density, which is favorable to the super-absorbent absorbing and retaining uid (Pourjava
et al., 2006). Low concentration of the cross-linker leads to low degree of cross linking, and it is hard for network structure to form, so
the water absorbency is low. However, when it is higher than the
best value, there are more cross-linking points and the pores become smaller in the network, which causes the macroscopic decrease of the absorbency.
3.1.4. Effect of neutralization degree of AA
Besides network structure, hydrophilic group is also an important factor on the absorbencies of polymer. The effect of neutralization degree of AA, which was neutralized by different amounts of
KOH, was studied, as shown in Table 4. It can be seen that the
water absorbency increased as the neutralization degree of AA increased, and reached the maximum when the neutralization degree was 85%. Then it decreased with further increase of the
neutralization degree of AA. So the optimum neutralization degree
was 85%. According to previous studies (Pourjava and Amini-Fazl,
2007), the colloid elasticity, ionic osmotic and afnity of polymer
toward water have an inuence on the swelling ability and absorbencies. The increasing neutralization of AA caused more hydrophilic groups to be grafted on the chain of the composite, thus
the network expanded, which was helpful to water absorption.
But when the neutralization degree was over 85%, more K+ ions

Z. Ma et al. / Bioresource Technology 102 (2011) 28532858

in the polymeric network would react with the COO group and
reduce the repulsion, thus resulting in the decrease of water
absorbencies.

3.1.5. Effect of the reaction temperature and time

In order to nd the effect of the reaction temperature on the
water absorbency, a series of SAR were prepared at different temperatures and the results were shown in Table 4. It indicated that
the water absorbency increased when temperature increased from
30 to 50 C, while it dropped when the temperature further increased. And the maximum water absorbency was 72.51 g/g in
the distilled water and 27.64 g/g in 0.9 wt.% NaCl solution at the
point of 50 C, respectively. The increasing temperature resulted
in more activation energy in the molecular and enhanced the radical formation and polymerization reaction, which would lead to
higher grafting yield and stronger water absorption capacity. However when the temperature was too high, a lot of monomer groups
would graft to the main chain and led to a close network structure,
which made it difcult for water to come in. Meanwhile many side
effects between the monomers would happen and the by-products
would have a bad effect on the absorbencies. So the best reaction
temperature was 50 C.
At last, Table 4 also demonstrated the effect of the reaction time
on the water absorbency. It indicated that the water absorbencies
increased with the reaction time, and reached the maximum at the
time of 5 h, then decreased when the time was longer than 5 h. For
this reason, more cross-linking reaction happened and more network structure formed when the time increased. But with a long
time reaction, many branched chains would be formed in the network structure, which could entangle with each other and obstruct
the expansion of the polymer (Chen et al., 2009). So it was hard for
water to enter into the network, and the water absorbency was
low.

3.2. FTIR spectroscopy

According to the FTIR spectra of the wheat straw and the SAR,
the absorption was observed at 3417 cm1 (hydroxyl stretch inuenced by hydrogen bond), 2918 cm1 (methylene), 1400 cm1
(carbonyl stretch) and 1068 cm1 (b-1,4-glycosidic bond), which
were characteristic absorptions in cellulose structures.
Comparison of absorption peaks of wheat straw and the SAR
revealed some change of absorption, which suggested that the
serial compositions of pulverized wheat straw had changed
during the reaction. The absorption peak between 1055.91 and
1165.93 cm1 indicated the existence of COC bond, which was
high in the spectrum of wheat straw but decreased in the spectrum
of the SAR. It suggested that the COC bond in the wheat straw
was fractured. In the spectrum of the SAR, the absorption peak at
1322.33 cm1 which was attributed to the CN bond of amide III
band, the peak at 1453 cm1 which resulted from the symmetrical
extension vibration of COO and the absorption peak at
1678 cm1 which showed the extension vibration of C@O of amide
I band were lager than those in the wheat straw. It indicated that
these three functional groups were grafted in the SAR after graft
copolymerization. The absorption peak of 3422 cm1, which came
from the hydroxyl stretch under the inuence of hydrogen bond,
was high in the SAR but low in the wheat straw. It can be learned
that after the reaction more OH were grafted on the carbon chain,
which resulted mostly from the increase of COOH. From the above
FTIR information, it can be concluded that AA, AM and DMDAAC
were grafted to the cellulose skeleton on the wheat straw during
the reaction with K2S2O8, (NH4)2Ce(NO3)6 with Na2SO3 as the initiator and MBA as the cross-linker.

2857

4. Conclusion
A super-absorbent composite was prepared by grafted copolymerization through AA, AM, DMDAAC and PTWS. The water absorbencies of the polymer synthesize under different conditions were
studied. Under the optimal synthesis condition, where the temperature was 50 C, the time was 5 h, the ratio between the monomers
and PTWS was m(PTWS):m(AA):m(AM):m(DMDAAC) = 1:4:2:1, the
weight rate of the initiator and the cross-linker were 1% and 0.2%,
and the neutralization degree of AA was 85%, the product attained
the best water absorbency of 133.76 g/g in distilled water and
33.83 g/g in 0.9 wt.% NaCl solution. And the synthesis of the SAR
is only a preliminary study. Some about the application and degradation of the product will be done in our future research work.

Acknowledgements
The authors are grateful to the support of the Chinese National
Foundation of Natural Sciences (21007034), the Foundation for
Young Excellent Scientists in Shandong Province (BS2009NY005),
Natural Science Foundation of Shandong Province (ZR2010EQ031),
Young Scientic and Technical Star Plan of Jinan City (20090215),
the Chinese National Foundation of Natural Sciences (50878121),
the 11th ve-year plan supported by the National Science and
Technology (2006BAJ08B05-2).

References
Bai, G., Li, Z., Li, J., 2003. The preparation and analysis of cellulose-graft super
absorbent resin. J. Shaanxi Univ. Sci. Technol. (Nat. Sci. Ed.). 21 (6), 3438.
Chen, Y., Liu, Y., Tan, H., et al., 2009. Synthesis and characterization of a novel
superabsorbent polymer of N,O-carboxymethyl chitosan graft copolymerized
with vinyl monomers. Carbohydr. Polym. 75, 287292.
Chu, M., Zhu, S.Q., Li, H.M., et al., 2006. Synthesis of poly(acrylic acid)/sodium
humate superabsorbent composite for agricultural use. J. Appl. Polym. Sci. 102,
51375143.
Davies, L.C., Novais, J.M., Martins-Dias, S., 2004. Detoxication of olive mill waste
water using super-absorbent polymers. Environ. Tech. 25 (1), 89100.
Dunford, N.T., Edwards, J., 2010. Nutritional bioactive components of wheat straw
as affected by genotype and environment. Bioresour. Technol. 101 (1), 422425.
Ende, M., Hariharan, D., Peppas, N.A., 1995. Factors inuencing drug and protein
transport and release from ionic hydrogels. React. Funct. Polym. 25, 127137.
Farag, S., Al-Afaleq, E.I., 2002. Preparation and characterization of saponied
delignied cellulose polyacrylonitrile-graft copolymer. Carbohydr. Polym. 48
(1), 15.
Guo, Y., Li, X., Li, C., et al., 2006. Preparation of agricultural superabsorbent resin by
wheat straw. Fine Chem. 23 (4), 3136.
Kamat, M., Malkani, R., 2003. Disposable diapers: a hygienic alternative. Indian J.
Pediatr. 70 (11), 879881.
Kiatkamjornwong, S., Mongkolsawat, K., Sonsuk, M., 2002. Synthesis and property
characterization of cassava starch grafted poly[acrylamide-co-(maleic acid)]
superabsorbent via g-irradiation. Carbohydr. Polym. 43 (14), 39153924.
Kim, J.H., Lee, J.H., Yoon, S.W., 2002. Preparation and swelling behavior of
biodegradable super-absorbent gels based on polyaspartic acid. J. Ind. Eng.
Chem. 8 (2), 138142.
Li, A., Zhang, J.P., Wang, A.Q., 2007. Utilization of starch and clay for the preparation
of superabsorbent composite. Bioresour. Technol. 98 (2), 119122.
Lanthong, P., Nuisin, R., Kiatkamjornwong, S., 2006. Graft copolymerization,
characterization, and degradation of cassava starch-g-acrylamide/itaconic acid
superabsorbents. Carbohydr. Polym. 66 (2), 229245.
Liang, R., Liu, M.Z., 2006. Preparation and properties of a double-coated slow-release
and water-retention urea fertilizer. J. Agr. Food Chem. 54 (4), 13921398.
Liu, Z., Miao, Y., Wang, Z., et al., 2009. Synthesis and characterization of a novel
super-absorbent based on chemically modied pulverized wheat straw and
acrylic acid. Carbohydr. Polym. 77 (1), 131135.
Peng, G., Xu, S.M., Peng, Y., et al., 2008. A new amphoteric superabsorbent hydrogel
based on sodium starch sulfate. Bioresour. Technol. 99 (3), 444447.
Pourjava, A., Amini-Fazl, M.S., 2007. Optimized synthesis of carrageenangraft-poly
(sodium acrylate) super-absorbent hydroxyl using the Taguchi method and
investigation of its metal ion absorption. Polym. Int. 56 (2), 283289.
Pourjava, A., Barzegar, S., Mahdavinia, G.R., 2006. MBA-cross-linked NaAlg/CMC as
a smart full-polysaccharide super-absorbent hydrogels. Carbohydr. Polym. 66
(3), 386395.
Pourjavadi, A., Mahdavinia, G.R., 2006. Superabsorbency, pH-sensitivity and
swelling kinetics of partially hydrolyzed chitosan-g-poly (acrylamide)
hydrogels. Turk. J. Chem. 30, 595608.

2858

Z. Ma et al. / Bioresource Technology 102 (2011) 28532858

Ray, S.S., Bousmina, M., 2005. Biodegradable polymers and their layered silicate
nanocomposites: in greening the 21st century materials world. Pro. Mater. Sci.
50, 9621079.
Rmond, C., Aubry, N., Crnier, D., et al., 2010. Combination of ammonia and
xylanase pretreatments: impact on enzymatic xylan and cellulose recover from
wheat straw. Bioresour. Technol. 101 (17), 67126717.
Sadeghi, M., Hosseinzadeh, H.J., 2008. Synthesis of starch-poly (sodium acrylate-coacrylamide) superabsorbent hydrogel with salt and pH-responsiveness
properties as a drug delivery system. J. Bioac. Compat. Polym. 23, 381404.
Sun, L., Wang, C., Lin, L., et al., 2007. Study on superabsorbent resin to saline solution
prepared by graft copolymerization with acrylic acid onto wheat straw. Appl.
Chem. Ind. 36 (12), 11941196.
Talebnia, F., Karakashev, D., Angelidaki, I., 2010. Production of bioethanol from
wheat straw: an overview on pretreatment, hydrolysis and fermentation.
Bioresour. Technol. 101 (13), 47444753.
Wang, Z., Liu, Z., 2006. The optimization of synthesizing graft copolymer of starch
with monomers. J. Wuhan Univ. Technol.-Mater. 21 (2), 8387.
Wang, Z., Liu, Z., 2004. Properties of super water absorbent polymers and their
applications in agriculture. Chin. J. Soil Sci. 6, 355.

Wu, L., Liu, M.Z., Liang, R., 2008. Preparation and properties of a double-coated
slow-release NPK compound fertilizer with super absorbent and waterretention. Bioresour. Technol. 99 (3), 547554.
Yi, J.Z., Zhang, L.M., 2008. Removal of methylene blue dye from aqueous solution by
adsorption onto sodium humate/polyacrylamide/clay hybrid hydrogels.
Bioresour. Technol. 99 (7), 21822186.
Yoshimura, T., Uchikoshi, I., Yoshiura, Y., et al., 2005. Synthesis and characterization
of novel biodegradable superabsorbent hydrogels based on chitin and succinic
anhydride. Carbohydr. Polym. 61, 322326.
Zhang, J., Wang, Q., Wang, A., 2009. Synthesis and characterization of chitosan-gpoly (acrylic acid)/attapulgite super-absorbent composites. Carbohydr. Polym.
68 (2), 367374.
Zhang, J., Wang, Q., Wang, A., 2007. Synthesis and characterization of chitosan-gpoly (acrylic acid)/attapulgite super-absorbent composites. Carbohydr. Polym.
68 (2), 367374.
Zhang, J., Li, A., Wang, A., 2006. Synthesis and characterization of multifunctional
poly(acrylic acid-co-acrylamide)/sodium humate super-absorbent composite.
React. Funct. Polym. 66 (7), 747756.