ARTICLE IN PRESS

Radiation Physics and Chemistry 69 (2004) 467471

A new hybrid nanocomposite prepared by graft

copolymerization of butyl acrylate onto chitosan in the
presence of organophilic montmorillonite
Li Yu, Liu Li, Zhang Weian, Fang Yuee*
Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026,
Peoples Republic of China
Received 22 September 2003; accepted 15 October 2003

Abstract
Organophilic montmorillonite (OMMT) was synthesized by cationic exchange between Na-MMT and tricetadecylmethyl ammonium bromide in an aqueous solution. A new nanocomposite consisting of poly(butyl acrylate)modied chitosan and OMMT was prepared by g-ray irradiation polymerization in acetic acid aqueous solution. The
degree of dispersion and the intercalation spacing of these nanocomposites were investigated using X-ray diffraction.
The enhanced thermal stabilities of nanocomposites were characterized by the thermal gravimetric analysis. The
improved mechanical properties of nanocomposites were characterized by static tensile studies and dynamic mechanical
analysis. The nanocomposites showed improved resistance to water absorption.
r 2003 Elsevier Ltd. All rights reserved.
Keywords: Nanocomposites; Chitosan; Butyl acrylate; g-ray irradiation

1. Introduction
Chitosan is a high molecular weight polysaccharide
composed mainly of b-(1,4)-linked 2-deoxy-2-aminod-glucopyranose units and partially of b-(1,4)-linked
2-deoxy-2-acetamido-d-glucopyranose. Because of its
biocompatibility, biodegradability and avirulence, chitosan has been used in many areas.
Interest in the modication of chitosan through graft
copolymerization has grown signicantly. The combination of natural and synthetic polymers via grafting yields
hybrid materials which may produce desirable properties. In previous studies, a number of different monomers have been grafted onto chitosan, these include
methylmethacrylate (Blair et al., 1987), acrylamide
(Yazdani-Pedram et al., 2002), 2-hydroxyethlymetha*Corresponding author. Tel.: +86-551-3601586; fax: +86551-3606763.
E-mail address: fye@ustc.edu.cn (F. Yuee).

crylate (El-Tahlawy and Hudson, 2001), N,N0 -dimethylaminoethylmethacrylate (Singh and Ray, 1997). As we
know there are no references in the literature to the
incorporation of clay into graft-modied chitosan.
Polymer/clay nanocomposites are of interest because
they combine the structure, physical and chemical
properties of both inorganic and organic materials.
Compared to the pure polymers these nanocomposites
demonstrate excellent properties such as improved
storage modulus (Yao et al., 2002), decreased thermal
expansion coefcients (Sun and Garces, 2002), reduced
gas permeability (Usuki et al., 2002), and enhanced ionic
conductivity (Wu and Lerner, 1993).
The clay that is most generally used is montmorillonite (MMT), which belongs to the 2:1 layered silicate. Its
crystal lattice consists of two silica tetrahedral sheets
fusing into an octahedral sheet. Isomorphous substitutions of Si4+ for Al3+ in the tetrahedral lattice and of
Al3+ for Mg2+ in the octahedral sheet can generate
negative charges that are counterbalanced by cations

0969-806X/$ - see front matter r 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.radphyschem.2003.10.012

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L. Yu et al. / Radiation Physics and Chemistry 69 (2004) 467471

such as Ca2+ and Na+. Many cationic surfactants can

be exchanged easily with the hydrated cations between
the layers and render the clay more organophilic than
the weak forces holding them together. As the
surface energy of the organoclay is much lower, many
polymers and monomers can intercalate within the
galleries easier.
In this work, we studied the modication of chitosan
by g-ray irradiation-induced graft copolymerization with
butyl acrylate in acetic acid aqueous solution containing
organophilic montmorillonite (OMMT). Chitosan was
used not only as a reactive component but also as a
cationic, polymeric surfactant (Hsu et al., 2002). Graft
copolymerization and the intercalation of BuA occurred
at the same time. The resulting nanocomposite emulsion
was used directly to prepare the sample with no
coagulation or separation. The purpose of this paper
was to investigate the effects of OMMT on the
structural, thermal, mechanical and water absorption
properties of the nal composites.

2. Experimental
2.1. Materials
Chitosan was obtained from San Huan Ocean
Biochemical Co. Ltd. (China). Its degree of deacetylation and the apparent viscosity were determined as
91.2% and 30 MPa s. Butyl acrylate was chemical grade.
Na+-MMT, with a cation exchange capacity (CEC)
value of 100 mmol/100 g, (Ling An Chemicals Co. Ltd.,
Hangzhou, China) was used without further purication. Tricetadecylmethyl ammonium bromide (TRIAB)
was supplied by Fei Xiang Chemicals Co. Ltd.,
Jiangshu, China.
The samples were irradiated at room temperature,
with the 2.22  1015 Bq 60Co g-ray source. The
irradiation doses were measured by ferrous sulfate
dosimeter.
2.2. Preparation of OMMT
The OMMT was prepared by cationic exchange
between Na+-MMT galleries and TRIAB in an aqueous
solution. The suspension solution containing 12.5 g
of Na+-MMT and 4.6 g TRIAB was mixed in
240 ml of distilled water. The suspension solution
was stirred at 75 C for 2 h, the exchanged MMT
was ltered and washed with distilled water until no
bromide ions was detected with 0.1 M AgNO3 solution.
Then the product was dried in vacuum oven at 60 C for
24 h. The OMMT obtained was ground with a mortar
and pestle and sieved through a 280 mesh copper
griddle.

2.3. Preparation of nanocomposites

An exact amount of chitosan was rst dissolved in 1%
acetic acid to prepare 2 wt% solution using a 50 cm3
stoppered bottle, followed by the addition of 3.0 g
monomer poly(butyl acrylate) (BuA). Then the required
amount of OMMT was added. After constant stirring
for 30 min, the system was deoxygenated by slow
bubbling of nitrogen gas through the solution for
10 min. The sample bottles were irradiated for a specied
time in a 60Co g-ray chamber applying continuous
stirring (dose: 10 kGy; dose rate: 60 Gy/min). After
completion of the reaction, the contents were cooled and
cast on a glass plate, the solvent was then evaporated
under an infrared lamp and sample lms were obtained.
The conversion of BuA was determined by the following
equation:
Conversion %
Sample film g  OMMT g  Chitosan g

100:
BuA used g

2.4. Percentage of grafting

The homopolymer of butyl acrylate was removed
from the sample lms by exhausive Soxhlet extraction
with toluene for 48 h. The grafting percentage are
dened and calculated as follows:
Grafting %

Wg  W  W0
 100;
W0

where Wg is weight of grafting copolymer, W0 is weight

of chitosan, W is weight of OMMT.
2.5. Characterization of nanocomposites
X-ray diffraction (XRD) patterns were obtained by
using a Rigaku D/max gA X-ray diffractometer using
graphite mono-chromatized Cu Ka radiation (l =
0.154178 nm). The scanning range was 1.510 with a
scanning rate of 2 /min.
The thermal gravimetric analysis (TGA) was conducted on a PerkinElmer TGA 7 Thermal Analyzer
under N2 ow. The heating rate was 10 C/min.
Dynamic mechanical analysis (DMTA) was carried
out on Rheometric Scientic DMTA IV at the frequency
of 1 Hz and at the heating rate of 2 C/min from 70 C
to 200 C at which the sample lost its dimensional
stability.
The tensile properties of sample lms were measured
using an instron tensile tester (UTM, 1112) under the
following conditions: crosshead speed 10 cm/min, gauge
length 3.0 cm, temperature 25 C, and relative humidity
65%.

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L. Yu et al. / Radiation Physics and Chemistry 69 (2004) 467471

2.6. Water absorption measurements

became organophilic and its basal spacing was

increased.

The clean, dried sample lms of known weights were

immersed in distilled water at 25 C until equilibrium
was reached (almost 24 h). The lms were removed,
blotted quickly with absorbent paper and then weighed.
The absorption percentage of these samples was
calculated using the equation
X %

469

M1  M0
;
M0

where M0 and M1 are the weight of dry and swollen

samples, respectively.

3. Results and discussion

3.1. Characterization of the Na+-MMT and OMMT
The preparation of the OMMT is a critical step in the
synthesis of polymerMMT nanocomposites. Firstly,
aliphatic amines are often used as they are very effective
agents for modifying clays. Secondly, the OMMT opens
the gallery spacing allowing monomers and polymers to
enter more easily. Fig. 1 shows XRD patterns of the
Na+-MMT and the OMMT. The intercalation of
polymer chains usually increases the interlayer spacing
relative to that of the pure MMT, leading to a shift in
the X-ray diffraction peak toward a lower angle. The
parameters were calculated from the observed peaks of
the angular position 2y by the Bragg formula: l =
2d sin y. The nite layer expansion associated with
intercalated structures resulted in a new reection that
corresponded to the layer gallery height of the intercalated nanocomposites. After intercalation, the XRD
data shows that the broad peak centered at 1.32 nm
corresponding to Na+-MMT was shifted to a new peak
at 3.75 nm for the OMMT. This conrms that MMT

3.2. XRD of nanocomposites

The X-ray diffraction curves for pure OMMT and
Poly (butyl-acrylate)-modied chitosan (CTS-PBuA)
nanocomposites with different OMMT contents are
shown in Fig. 2. In this gure, the pure CTS-PBuA does
not exhibit any diffraction peak, but when the amount
of the OMMT dispersed in CTS-PBuA is only 3 wt%,
there is a diffraction peak is at 2y = 1.8 (d = 4.78 nm),
which means that the intercalation has occurred and the
intercalated nanocomposites have been formed. With
the amount of the OMMT increased to 7 wt%, there was
no distinct shift, indicating that the distance between the
sheets of nanocomposite was not affected by the amount
of the OMMT.
3.3. Influence of OMMT on monomer conversion and
grafting percentage
Fig. 3 shows the relationship between radiation dose
and monomer conversion. It can be seen that below
2 kGy, conversion of BuA dramatically increases with
increasing dose. After the conversion of BuA reaches
about 80%, the increasing viscosity of system and the
lower monomer concentration lead to the decrease of
polymerization rate. Under the same conditions, due to
the restricted movement of BuA and the inhibition of
the propagating chain radicals in the OMMT galleries,
the polymerization rate of BuA was decreased. Therefore, the conversion of BuA in the OMMT system was
lower than in the pure system.
Under the same conditions (dose: 10 kGy; dose rate:
60 Gy/min; BuA conversion: 95%) the inuence of
OMMT on the grafting percentage of PBuA-modied

Intensity

Intensity

a: 0% OMMT
b: 3% OMMT
c: 5% OMMT
d: 7% OMMT
e: pure OMMT
e

OMMT
+

Na -MMT

c
b
a

3
2

2 (degrees)
Fig. 1. XRD patterns of Na+-MMT and OMMT.

2 (degrees)
Fig. 2. XRD patterns of pure OMMT and nanocomposites
with different OMMT contents.

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L. Yu et al. / Radiation Physics and Chemistry 69 (2004) 467471

470

degradation of the whole material. Evidently, at the

second stage, the decomposition onset temperature of
the CTS-PBuA nanocomposites shifted towards higher
temperatures compared to CTS-PBuA, indicating the
enhancement of thermal stability of the nanocomposites.
It may be due to the fact that MMT is inorganic
material with high thermal stability and great barrier
properties and can prevent the heat from transmitting
quickly and can limit the continuous decomposition of
the nanocomposites.

100

60

40

0% OMMT
7% OMMT

20

3.5. DMTA and static tensile testing of nanocomposites

0
0

10

11

12

Radiation dose (kGy)

Fig. 3. The monomer conversion vs. radiation dose of CTSPBuA (m) and CTS-PBuA nanocomposite with 7 wt% OMMT
(); dose rate: 60 Gy/min.

a: 0%
b: 3%
c: 5%
d: 7%
d

100

Weight loss (%)

80

60

a
40

20

0
100

200

300

400

Temperature (C)
Fig. 4. TGA thermograms of CTS-PBuA and CTS-PBuA
nanocomposites with the different OMMT contents.

chitosan was also investigated and we found that below

7 wt% the percentage of grafting did not change
signicantly with increasing OMMT concentration.
Beyond 7 wt% (OMMT conc.) there is a marked
decrease in the grafting percentage. This is attributed
to the fact that the diffusion of BuA and propagating
chain radicals into chitosan matrix was inhibited under a
higher OMMT concentration.

Fig. 5 shows the storage modulus, E0 of the CTSPBuA and CTS-PBuA nanocomposites with different
OMMT contents. Compared with the CTS-PBuA, the
CTS-PBuA nanocomposite with 3 wt% OMMT exhibited an enhanced E0 . The CTS-PBuA nanocomposites
with more than 3 wt% OMMT did not show an increase
in E0 , and in fact the E0 decreased below the glass
transition temperature of PBuA. A similar phenomenon
was also observed in the tensile testing results (Table 1).
This may be explained as follows: the introduction of
OMMT can form many cross-linking points which
strengthen the interaction of the MMT and PBuA;
when the concentration of OMMT is higher, some
MMT forms clusters in the composites and these clusters
may act as stress concentrating points resulting in a
decrease in E0 .
The loss tangent tan y for these nanocomposites is
shown in Fig. 6. CTS-PBuA shows a narrow peak
around 50 C and a broad peak at 100 C. The former
peak corresponds to the glass transition temperature
(Tg) of PBuA. The second peak may be due to some
transition of chitosan. With the increase of OMMT
concentration, two peaks of CTS-PBuA nanocomposites

800

a: 0%
b: 3%
c: 5%
d: 7%

1000

E' (mPa)

conversion

80

600

400

3.4. Thermal properties

200

The TGA thermograms of CTS-PBuA and CTSPBuA nanocomposites with different OMMT contents
are presented in Fig. 4. The thermal degradation prole
of CTS-PBuA exhibit two main decomposition stages
with one starting at around 270 C and another starting
at around 350 C. The rst stage is attributed to the
degradation of chitosan. The second stage is the

0
-50

50

100

150

200

Temperature (C)
Fig. 5. The trend of the storage modulus E0 of CTS-PBuA
and CTS-PBuA nanocomposites with the different OMMT
contents.

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L. Yu et al. / Radiation Physics and Chemistry 69 (2004) 467471
Table 1
Tensile testing of CTS-PBuA nanocomposites

4. Conclusion

OMMT conc (wt%)

0
3
5
7
Tensile strength (mPa)
3.09
3.91 2.89 2.33
Elongation at break (%)
36
39
33
30
Tensile modulus (25 C) (mPa) 103
146
97
80

0.40

a: 0%
b: 3%
c: 5%
d: 7%

0.35

tan

0.30

a
b

0.25

0.20
0.15

a
0.10

471

A new hybrid nanocomposite was prepared by graft

copolymerization of butyl acrylate onto chitosan in
acetic acid aqueous solution containing OMMT and
direct casting of the resulting emulsions into lms. XRD
shows that the layers of MMT are intercalated and
orderly dispersed in this nanocomposite. The nanocomposites exhibit an enhancement of the storage
modulus and the glass transmission temperature. Relatively small amounts of OMMT (3 wt%) can provide
composites with substantial improvements in mechanical and thermal properties, and resistance to water
absorption. Because synthesis and molding methods are
environmentally benign and simple, these nanocomposites may have many potential applications in industry
and agriculture such as packaging lms and seed
coating.

0.05
-50

50

100

150

200

Acknowledgements

Temperature (C)
Fig. 6. The tan y vs. temperature of CTS-PBuA and CTSPBuA nanocomposites with the different OMMT contents.

Thanks for the nancial support by the National

Natural Science Foundation of China (20274044).

Table 2
Water absorption of CTS-PBuA nanocomposites

References

OMMT conc. (w%)

Water absorption (%) 24 h

0
133.2

3
82.2

5
80.5

7
75.6

are shifted to higher temperature, compared to CTSPBuA. The Tg of PBuA in the nanocomposite with
7 wt% OMMT is about 10 C more than that in the pure
CTS-PBuA. It means the interaction between the MMT
and PBuA limits the segmental movement of the PBuA.
We do not at present understand the origin of the second
peak, but according to the result of a previous report
(Ratto et al., 1996), it may be due to the signicant
rearrangement of bond structure taking place within the
acetamide and amine bond regions of chitosan. The
introduction of OMMT may inhibit the rearrangement
of bond structure. Hence, the transition temperature of
chitosan is increased.
3.6. Water absorption studies
Table 2 shows the percentage of water absorption for
the CTS-PBuA nanocomposites. It shows an decreasing
trend of water absorption percentage with the increase
of OMMT concentration. This is probably because that
OMMT can form large numbers of cross-linking points
which results in a crosslinking network structure. As a
consequence the water absorption is reduced.

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