Carbohydrate Polymers 75 (2009) 665669

Contents lists available at ScienceDirect

Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

New intercalated layer silicate nanocomposites based on synthesized starch-g-PCL

prepared via solution intercalation and in situ polymerization methods:
As a comparative study
Hassan Namazi a,b,*, Mohsen Mosadegh a, Abbas Dadkhah a
a
Research Laboratory of Dendrimers and Nanopolymers, Faculty of Chemistry, University of Tabriz, P.O. Box 51666, Tabriz EA, Iran
b
Center of Excellence for New Materials and Clean Chemistry, University of Tabriz, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Starch-g-polycaprolacton (Starch-g-PCL) nanocomposites have been prepared with graft polymerization
Received 25 June 2008 through in situ ring-opening polymerization of e-caprolacton in the presence of starch and Sn(Oct)2
Received in revised form 5 September 2008 (Tin(II) 2-ethyl hexanoate) as an initiator/catalyst. A surface-modied montmorillonite by dimethyl
Accepted 8 September 2008
(hydrogenated tallow alkyl) ammonium cation, was used. In fact, the related nanocomposites prepared
Available online 18 September 2008
via two methods in solution and in situ with introducing different amount of loading clay. The effect
of swelling time on d-spacing of silicate layers was investigated and the obtained nanocomposites were
Keywords:
analyzed using X-ray diffraction technique. The morphology of the synthesized nanocomposites exam-
Nanocomposite
Organo clay
ined using Scanning Electron Microscopy (SEM) and also the thermal degradation behavior of the pre-
Starch-graft polymerization pared nanocomposites accomplished with using TGA.
In situ polymerization 2008 Elsevier Ltd. All rights reserved.

1. Introduction sorbitol (Gaudin, Lourdin, Forssell, & Colonna, 2000) and glycerol,
considerably improves mechanical properties. Even though,
In order to develop an environmentally friendly material, starch lms have poor mechanical properties when compared to
many efforts have been made to solve problems generated by those of synthetic polymers. This is due to their hydrophilic nat-
plastic wastes, particularly by one-time-use disposable commod- ure and thus their sensitivity to moisture content, a factor that is
ity materials. Most of the research attention was focused on the difcult to control. In order to improve mechanical properties and
replacement of Petro-based commodity plastics in a cost-effective water resistance, starch has been modied (Morikawa &
manner by biodegradable material with competitive mechanical Nishinari, 2000; Curvelo, de Carvalho, & Agnelli, 2001; Mani,
properties. Biopolymers have been considered as most promising Tang, & Bhattacharya, 1998; Rutot, Degee, Nayaran, & Dubois,
materials for this purpose. Among natural polymers, starch has 2000; Matzinos, Tserki, Kontoyiannis, & Panayiotou, 2002; Mani
been considered as one of the most promising candidates for & Bhattacharya, 2001; Dufresne, 2006) by blending with synthetic
the future, primarily because of an attractive combination of or natural polymers and modied with aliphatic polyesters, such
availability, price and performance. Starch consists of the linear as PCL, poly (hydroxyl butyrate), poly lactic acid and poly (gly-
a-glucan amylose and highly branched amylopectin. Starches in colic acid) (Namazi & Dadkhah 2008; Wang & Gross, 1998).
their native forms, are organized into semi crystalline granules Among them poly (e-caprolacton) is a particularly promising
(Hizukuri, Takeda, Yasuda, & Suzuki, 1981; Thompson, 2000; polymer. It is a plastic with high exibility and also is biodegrad-
Hoover, 2001; Grard, Planchot, Colonna, & Bertoft, 2000). Several able. Recently a new class of hybrid materials of polymers and
studies have been carried out on starch-based lms obtained by layered silicates has emerged (Dietsche & Mulhaupt, 1999; Lim
melt processing or casting lm of a solution or gel with addition & Park, 2001). This class of materials have improved the material
of a plasticizer (Garca, Martino, & Zaritzky, 2000; Kalambur & properties due to the high aspect ratio and easy phase-to-phase
Rizvi, 2006). The addition of water or other plasticizers such as energy transfer, even at very low ller concentration, if the ller
is uniformly and completely dispersed in the host matrix (LeBar-
on et al.,1999; Lee, Hur, Yang, Lim, & Kim, 2006; McGlashan &
Halley, 2003; Ray & Okamoto, 2003). The introduction of inor-
ganic llers that commonly used nanoclays includes montmoril-
* Corresponding author. Address: Research Laboratory of Dendrimers and
Nanopolymers, Faculty of Chemistry, University of Tabriz, P.O. Box 51666, Tabriz
lonite, a 2:1 phylosilicate. Nanoclays have a stacked platelet
EA, Iran. Tel.: +98 411 3393121; fax: +98 411 3340191. structure with each platelet having a thickness of approximately
E-mail addresses: namazi@tabrizu.ac.ir, hnamazi2001@yahoo.com (H. Namazi). 1 nm and lateral dimensions on the order of micrometers.

0144-8617/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbpol.2008.09.006
666 H. Namazi et al. / Carbohydrate Polymers 75 (2009) 665669

Unmodied nanoclays have a hydrophilic interlayer between each Table 2

platelet that can be rendered more hydrophobic through a cation Preparation nanocomposites with solution intercalation method

exchange process involving alkylammoniums. Starch has been Samples Loading clay (wt%) Starch-g-PCL (g) Reaction time (h)
lled with layered silicates and an improvement in mechanical C15A 100 0 0
and barrier properties was observed (Park et al., 2002; Pandey NC1 2.5 1 5
& Singh, 2005; Kalambur & Rizvi, 2004; Avella et al., 2005; Pandey NC2 2.5 1 20
et al., 2005). In the present work we investigated the preparation NC3 5 1 5
NC4 5 1 20
of starch-g-PCL nanocomposites with Closite 15A (montmorillon- NC5 7.5 1 5
ite surface-modied by dimethyl hydrogenated tallow alkyl NC6 7.5 1 20
ammonium cation) and in fact related nanocomposites were pre- NC7 10 1 5
pared through two methods in solution intercalation and in situ NC8 10 1 20
polymerization with different amount of loading clay. The disper-
sion of clay into starch-g-PCL matrix examined using XRD and
morphology of some samples investigated through SEM.
Table 3
2. Experimental Preparation of starch-g-PCL nanocomposites by in situ polymerization method
(starch/clay: 50/50)

2.1. Materials Samples Loading clay (wt%) Swelling time (h) T(C) Reaction time (h)
NC9 5 1.5 150 5
Potato starch was obtained from Merck. (Germany) Organo clay NC10 5 18 150 5
(Closite 15A) was from Southern Clay Product (USA), having CEC of NC11 5 18 100 20
NC12 5 48 100 20
125 meq/100 g clay. Stannous 2-ethylhexanoate Sn(Oct)2 and e-
caprolacton were purchased from Fluka.

2.2. Preparation of starch-g-PCL 3. Results and discussion

In a typical experiment, 3 g of e-caprolacton was added to 3 g of 3.1. X-ray diffractions

starch in a 100 ml round-bottomed ask equipped with a stirrer
and a rubber septum and previously purged with nitrogen (Dubois, The samples were prepared through the ring-opening poly-
Krishnan, & Narayan, 1999). A determined amount of Sn(Oct)2 was merization as shown in Scheme 1 and FT-IR data analysis was
then introduced via a conditioned syringe at the desired tempera- conrmed the formation of grafting (Chen et al., 2005). The pat-
ture (see Table 1). Polymerization was stopped by fast cooling to tern of X-ray diffraction of the samples was obtained by Siemens
room temperature and monomer conversion determined by selec- diffractometer with Cu-ka radiation at 35 kV in the scan range of
tive precipitation of the polymeric fraction and starch in heptane. 2h from 2 to 30. The d-spacing was calculated by Braggs equa-
The homopolymers was extracted in toluene after 24 h at room tion where k was 0.154 nm. This dispersion extent of silicate lay-
temperature and the characteristic peaks at 1730 and 3400 cm 1 ers has typically been elucidated by XRD, which allow a direct
FT-IR spectrum was conrmed the graft formation of e- evidence of polymer chain connement into the silicate gallery.
caprolactone. The presence of narrow peaks for all samples except pattern of
pure starch is an evidence of the ordinary in clay layers and con-
2.3. Preparation of starch-g-PCL nanocomposites with solution rming the nite diffusion of copolymer chains with a repeat
intercalation method distance of few nanometers. It is generally thought that the
polymer enters the organo clay galleries and forces apart the
The different amount of C15A dispersed and swelled in 10 ml platelets (intercalation). As more polymers enter the gallery,
toluene for 3 h. Then 3 g starch-g-polycaprolacton was added for the platelets become disordered, thus causing broader peak
2 h at 100110 C with continuous stirring and the products was and a wider distribution of such peak. Starch has hydrophilic
then poured on dishes and solvent evaporated at 5060 C. The property in comparison to organo clay which is hydrophobic.
prepared samples are shown in Table 2. The resulted copolymer from grafting polycaprolacton on starch
showed a hydrophobic property and its compatibility increased
2.4. Preparation of starch-g-PCL nanocomposites through in situ with organo clay due to reaction time of 20 h which caused a
polymerization method better yield in comparison to 5 h reaction time. The samples
NC2, NC4, NC6 and NC8 are related to the reaction time of
The 5 wt% C15A swelled and dispersed in 3 g e-caprolacton 20 h and samples NC1, NC3, NC5 and NC7 for 5 h reaction time.
for 18 h under nitrogen atmosphere, then 3 g starch was added The results of X-ray diffraction analyzes which are shown in Ta-
for 3 h with continuous stirring and a determined amount of ble 4 indicating that the rst series of copolymer samples have
Sn(Oct)2 was then introduced via a conditioned syringe at the been better diffused into gallery of organo clay (C15A) with
desired temperature. Polymerization stopped by fast cooling at interlayer spacing of d = 3.15 nm in comparison with second ser-
room temperature. Methods of sample preparations are shown ies of copolymer samples.
in Table 3. The obtained d-spacing of XRD patterns showed that the en-
trance of copolymer into gallery of organo clay and formation the
intercalated structure for the prepared nanocomposites. The high-
Table 1
est increased d-spacing related to NC4 with its loading amount of
Synthesis of Starch/PCL (50/50 wt%) clay 5 wt% and 20 h reaction time. In all of the prepared samples
by in situ method the C15A loading was 5 wt%. In sample NC9 d-
Sn content (wt%) T(C) Reaction time (h) Conversion monomer
spacing decreased due to 2 h swelling time of monomer in organo
0.4 100 20 99.5 clay and addition of starch in 30 min time. The reason of this result
0.2 150 5 98
could be related to the little diffusion of monomer into layers
 H. Namazi et al. / Carbohydrate Polymers 75 (2009) 665669 667

H St
O O
O
St O Sn(Oct)2
O
St OH + Sn(Oct)2 HO Sn(Oct)2

St-(OCOCH2CH2CH2CH2)-OCOCH2CH2CH2CH2OH

Scheme 1. The reaction route of graft polymerization on starch granules.

Table 4
Results of X-ray diffraction

Samples Loading clay wt% 2h d-Spacing ()

C15A 100 2.81 31.5
NC1 2.5 2.66 33.22
NC2 2.5 2.26 39.16
NC3 5 2.60 34.03
NC4 5 2.25 39.31
NC5 7.5 2.66 33.30
NC6 7.5 2.43 36.42
NC7 10 2.69 32.82
NC8 10 2.26 39.03
NC9 5 2.98 29.66
NC10 5 2.50 35.35
NC11 5 2.38 37.16
NC12 5 2.49 35.47

which allows the polymerization of PCL to take place out of the

internal area of layers and pushing the polymer chains into layers
and therefore, d-spacing decrease. As shown in Fig. 1 for the sam-
ple NC10 the swelling time was increased from 2 h to 18 h and X-
ray results showed one peak in 2h = 2.5. The sample NC11 with
2h = 2.38 by swelling time of 18 h that was prepared in 20 h reac-
tion time at 100 C. In NC12 sample swelling time also was in- Fig. 2. Granules of pure potato starch.
creased to 48 h and d-spacing = 3.47 nm was observed. Therefore,
according to the X-ray data d-spacing was increased with changing
reaction time, temperature and swelling time.

3.2. Scanning electron microscopy

For the prepared nanocomposites morphology and their

changes was investigated by using SEM. Image of granules of

Fig. 1. Comparison of XRD patterns for different samples. Fig. 3. Starch-g-PCL/5 h reaction time.
668 H. Namazi et al. / Carbohydrate Polymers 75 (2009) 665669

starch are shown in Fig. 2. Dimensions of granules are between 10

to several hundreds. SEM images related to starch-g-PCL with 5
and 20 h reaction times are shown in Figs. 3 and 4, respectively.
As shown in these images the reaction yield increased with
using PCL for graft reaction on starch when the reaction time in-
creased (Mani et al., 1998). In nanocomposite samples the shape
of granules completely changed. The images of NC10 and NC4
are shown in Figs. 5 and 6, respectively.3.3. Thermal gravimetry
analyzes

Thermal degradation behavior of prepared nanocomposite

samples was studied through thermo gravimetric analysis TGA
under an N2 ow at a heating rate of 20 C/min and Fig. 7 shows

Fig. 6. Starch-g-PCL/clay (NC4).

TGA values and the data of related TGA is shown in Table 5 for
the samples. The curves show that the decomposition of the
samples takes place at different temperature. For starch alone
the weight lost starts at 260 C however, with rising grafting
PCL chains on starch it happens at 360 C. Also the thermal
decomposition curves related to CN4 and CN11 nanocomposite
samples shift towards the higher temperature in comparison to
starch. The thermo gram shows that degradation of CN11and
CN4 samples have been started in order at 282 C and 323 C.
This shift to higher temperature might be explained by a lower
permeability/diffusivity of oxygen and volatile degradation prod-
Fig. 4. Starch-g-PCL / 20 h reaction time.
uct through the sample as the result of barrier properties. At
about 600 C, all the curves merge together and became at
which indicates the presence of inorganic residue (i.e., AL2O3,
MgO and SiO2) (Yu, Lin, Yeh, & Lin, 2003). Therefore, as seen
the decomposition product is mainly due to the polymer matrix
and not from the clay particles.

4. Conclusions

Results of XRD analyses showed the best diffusion and inter-

calation of copolymer into galleries of organo clay that occurs
through solution intercalation in comparison with in situ meth-
od. Because organo clay is compatible with copolymer starch-g-
PCL while, it is not compatible with pure starch. Images of SEM
showed a good yield for graft polymerization at 20 h reaction
time and morphology of the granules had been changed. TGA
investigations showed that with grafting caprolacton on starch
thermal stability of both grafted starch and also their nanocom-
posites improved in comparison with thermal stability of pure
starch.

Acknowledgments

We thank Department of Physics and Department of Material

Engineering in the University of Tabriz for XRD analysis and SEM
Images and also SUT for TGA analysis. Authors also greatly
acknowledge the University of Tabriz for the nancial support of
Fig. 5. Starch-g-PCL/clay (NC10). this work.
 H. Namazi et al. / Carbohydrate Polymers 75 (2009) 665669 669

Fig. 7. Thermograms of starch, NC11, starch-g-PCL (20 h), NC4.

Table 5 LeBaron, P. C., Wang, Z., & Pinnavaia, T. J. (1999). Polymer-layered silicate
Collected data from TGA nanocomposites: an overview. Applied Clay Science, 15, 1129.
Lee, S. S., Hur, M. H., Yang, H., Lim, S., & Kim, J. (2006). Effect of interfacial attraction
Sample Loading clay (%) T (C) of loss 10 wt% T (C) of loss 50 wt% on intercalation in polymer/clay nanocomposites. Journal of Applied Polymer
Science, 101, 27492753.
Starch 0 258 326
Lim, Y. T., & Park, O. (2001). Phase morphology and rheological behavior of polymer/
Starch-g-CL 0 307 352 layered silicate nanocomposites. Rheologica Acta, 40, 220229.
NC4 (solvent) 5 316 354 Mani, R., & Bhattacharya, M. (2001). Properties of injection moulded blends of
NC11(in situ) 5 262 352 starch and modied biodegradable polyesters. European Polymer Journal, 37(3),
515526.
Mani, R., Tang, J., & Bhattacharya, M. (1998). Synthesis and characterization of
starch-graft-polycaprolacton as compatibilizer for starch/polycaprolacton
References blends. Macromolecular Rapid Communications, 19, 283286.
Matzinos, P., Tserki, V., Kontoyiannis, A., & Panayiotou, C. (2002). Processing and
characterization of starch/polycaprolacton products. Polymer Degradation and
Avella, M., Vlieger, J. J. D., Errico, M. E., Fischer, S., Vacca, P., & Volpe, M. G. (2005).
Stability, 77, 1724.
Biodegradable starch/clay nanocomposite lms for food packaging applications.
McGlashan, S. A., & Halley, P. G. (2003). Preparation and characterization of
Food Chemistry, 93, 467474.
biodegradable starch-based nanocomposite materials. Polymer International, 52,
Chen, L., Ni, Yu., Bian, Xi., Qiu, Xu., Zhuang, Xi., Chen, Xu., et al. (2005). A novel
17671773.
approach to grafting polymerization of caprolactone on to starch granules.
Morikawa, K., & Nishinari, K. (2000). Rheological and DSC studies of gelatinization of
Carbohydrate Polymers, 60, 103109.
chemically modied starch heated at various temperatures. Carbohydrate
Curvelo, A. A. S., de Carvalho, A. J. F., & Agnelli, J. A. M. (2001). Thermoplastic starch
Polymers, 43, 241247.
cellulosic bers composites: preliminary results. Carbohydrate Polymers, 45,
Namazi, H., & Dadkhah, A. (2008). Surface modication of starch nanocrystals
183188.
through ring opening polymerization of e-caprolactone and investigation of
Dietsche, F., & Mulhaupt, R. (1999). Thermal properties and ammability of acrylic
their microstructures. Journal of Applied Polymer Science, 40(4), 24052412.
nanocomposites based upon organophilic layered silicates. Polymer Bulletin, 43,
Pandey, J. K., & Singh, R. P. (2005). Green nanocomposites from renewable
395402.
resources: Effect of plasticizer on the structure and material properties of
Dubois, Ph., Krishnan, M., & Narayan, R. (1999). Aliphatic polyester-grafted starch-
clay-lled starch. StarchStarke, 57, 815.
like polysaccharides by ring-opening polymerization. Polymer, 40, 30913100.
Pandey, J. K., Kumar, A. P., Misra, M., Mohanty, A. K., Drzal, L. T., & Singh, R. P. (2005).
Dufresne, A. (2006). Comparing the mechanical properties of high performances
Recent advances in biodegradable nanocomposites. Nanoscience and
polymer nanocomposites from biological sources. Journal of Nanoscience and
Nanotechnology, 30, 497525.
Nanotechnology, 6, 322330.
Park, H. M., Li, X., Jin, Ch., Park, Ch., Cho, W., & Ha, Ch. (2002). Preparation and
Garca, M. A., Martino, M. N., & Zaritzky, N. E. (2000). Microstructural
properties of biodegradable thermoplastic starch/clay hybrids. Macromolecular
characterization of plasticized starch-based lms. StarchStarke, 52, 118124.
Materials and Engineering, 553558.
Gaudin, S., Lourdin, D., Forssell, P. M., & Colonna, P. (2000). Antiplasticisation and
Ray, S. S., & Okamoto, M. (2003). Polymer/layered silicate nanocomposites: a
oxygen permeability of starchsorbitol lms. Carbohydrate Polymers, 43, 3337.
review from preparation to processing. Progress in Polymer Science, 28,
Grard, C., Planchot, V., Colonna, P., & Bertoft, E. (2000). Relationship between
15391641.
branching density and crystalline structure of A- and B-type maize mutant
Rutot, D., Degee, Ph., Nayaran, R., & Dubois, Ph. (2000). Aliphatic polyester-grafted
starches. Carbohydrate Research, 326, 130144.
starch composites by in situ ring opening polymerization. Composite Interfaces,
Hizukuri, S., Takeda, Y., Yasuda, M., & Suzuki, A. (1981). Multi-branched nature of
7, 215225.
amylose and the action of debranching enzymes. Carbohydrate Research, 94,
Thompson, D. B. (2000). On the non-random nature of amylopectin branching.
205215.
Carbohydrate Polymers, 43, 223239.
Hoover, R. (2001). Composition, molecular structure, and physicochemical
Wang, L. M., & Gross, R. A. (1998). Reactive compatibilization of biodegradable
properties of tuber and root starches: a review. Carbohydrate Polymers, 45,
blends of poly(lactic acid) and poly(e-caprolacton). Polymer Degradation and
253267.
Stability, 59, 161168.
Kalambur, S. B., & Rizvi, S. Sh. (2004). Starch-based nanocomposites by reactive
Yu, Y. H., Lin, Ch. Y., Yeh, J. M., & Lin, W. (2003). Preparation and
extrusion processing. Polymer International, 53, 14131416.
properties of poly(vinyl alcohol)clay nanocomposite materials. Polymer,
Kalambur, S. B., & Rizvi, S. Sh. (2006). An overview of starch-based plastic blends
44, 35533560.
from reactive extrusion. Journal of Plastic Film and Sheeting, 22, 3958.