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Reactive Extrusion
INTRODUCTION
Plastics obtained from petrochemical sources generally
have lifetimes of hundreds of years when buried in typical
solid waste sites, and thus have posed signicant environmental threats [1]. These plastics have contributed 1725%
of the volume of waste being land lled [2]. Hence, recently, much research has concentrated on the development
of environmental-friendly biodegradable plastics obtained
from various natural renewable resources including starch,
cellulose, poly(hydroxyalkanoates), and poly(lactic acid).
Three main classes of biodegradable polymers have been
recognized. The rst class consists of synthetic polymers
sourced from nonrenewable resources with vulnerable
groups susceptible to hydrolysis attack by microbes. The
second class of materials is composed of naturally-occurring bacterial polymers such as polyhydroxybuterates
(PHB), polyhydroxyvalerates (PHV), and polyhydroxybuterates-co-valerates (PHB/V). Although polyhydroxyalkanoates are truly renewable and biodegradable, the determination of processing parameters and high production
as dicumyl peroxide (DCP), benzoyl peroxide, and di-tertbutyl peroxide (DBP) for grafting biodegradable polybutylene succinate (PBS) with starch in presence of MA as a
crosslinking agent. Sailaja and Chanda [17] have used MAgrafted polyethylene (PE) for preparing PE-starch blends in
presence of benzoyl peroxide as initiator. Ceric ammonium
nitrate (CAN) is another initiator commonly used during
reactive grafting. Luftor et al. [18] studied the kinetics of
graft polymerization of acrylonitrile onto sago starch using
CAN as initiator. These works suggested the use of other
crosslinking agents such as phthalic anhydride and dodecyl
succinic anhydride in the presence of initiators to facilitate
grafting reactions.
Of all the methods used to achieve compatibilization in
starchpolyester blends, reactive extrusion (REX) is a wellutilized technique as it combines the traditionally separated
chemical processes (polymer synthesis and/or modication)
and extrusion (melting, blending, structuring, devolatilization, and shaping) into a single process carried out in the
extruder [19]. Using REX, modied polymer can be obtained in a ready-to-use form at the die.
Unmodied starch-based thermoplastics generally have
higher viscosities and poor melt properties than traditional
synthetic polymers that make them difcult to process.
Also, starch and synthetic polymers are generally thermodynamically dissimilar in nature, and hence are incompatible unless a compatibilizer is used. In REX of crosslinking
dissimilar polymers, free-radical initiation plays a predominant role. However in the extruder, mechanochemistry, by
itself, is not powerful enough for free-radical generation in
such grafting reactions. Hence, in this study, we have attempted to graft MA to a biodegradable polyester in presence of a free-radical initiator during stage-one of extrusion,
and further crosslinked MA-grafted polyester to starch during a second extrusion stage. We used different temperature
proles during the REX process. Should the compatibilized
blends exhibit improved mechanical properties, determination of interfacial tension and controlling the interfacial
properties of such blends will lead us on the path to developing well-controlled biodegradable blends with tailorable
mechanical properties.
MATERIALS
EnPol, a biodegradable thermoplastic polyester, was
obtained from IRe Chemical, Korea. Two types of starch
with different levels of amylopectin-to-amylose ratios were
used in a preset blend ratio in all formulations. The rst was
a low-amylose common waxy wheat starch and the other a
high-amylose, chemically-modied maize starch (hydroxypropylated starch). The second has a lower gelatinization temperature than the rst and is able to withstand
higher processing temperatures. Both starches were sourced
from Penford (Australia). These starches were blended together with plasticizers in accordance with the patents [20,
21] held by the Cooperative Research Centre for International Food Manufacture and Packaging Science and a
POLYMER ENGINEERING AND SCIENCE2006
249
TABLE 1.
TABLE 2.
extrusion.
S (wt%)
PEst (wt%)
MA (wt%)
DCP (wt%)
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
0.0
0.5
0.5
0.5
0.5
1.0
1.0
1.0
1.0
1.0
1.5
1.5
1.5
1.5
1.5
0.0
0.3
0.5
0.8
1.2
0.0
0.3
0.5
0.8
1.2
0.0
0.3
0.5
0.8
1.2
Die
Zone9
Zone8
Zone7
Zone6
Zone5
Zone6
Zone5
Zone4
Zone3
Zone2
Zone1
Stage-1
Stage-2
100
120
160
180
180
180
180
180
180
180
150
120
100
120
160
180
180
180
180
180
180
180
150
120
Grafting Procedure
The grafting reactions were carried out in a laboratory
scale PRISM co-rotating twin-screw extruder with a barrel
length to diameter ratio of 40:1, a screw diameter of 16 mm
and eight heating zones. The composition of SPF and the
polyester was maintained at 40:60 (wt%) in all the blends.
The rst step was the preparation of maleated polyester.
From initial trials we found that the color of the extrudate
varied as the composition of MA was increased (0.5% MA,
white; 1% MA, light-pink; 1.5% MA, dark-pink; 2% MA,
brown; 3% MA, brownish-black; 5% MA, black). Maleated
polyesters with MA concentration of more than 2% were
found to be unsuitable for compounding with starch. Therefore, after optimizing the process, three different compositions of MA (0.5, 1, 1.5%) and four different compositions
of DCP (0.3, 0.5, 0.8, 1.2%) were selected. The temperature
proles for stage-1 and stage-2 of extrusion are shown in
Table 2. EnPol was dried under vacuum for 24 h prior to the
day of extrusion. MA and DCP were used in their powder
form. A mixture of polyester, MA, and DCP was introduced
using a mechanical feeder at a feed rate of 0.38 kg/h. Screw
250
Tensile Testing
The strands of different blends were subjected to tensile
testing using an Instron Universal tensile testing machine
(model 5584). A 5 KN load cell was used for determining
important properties such as stress at break, strain at break,
Youngs modulus, and stress and strain at maximum load. A
grip separation of 50 mm, crosshead speed of 5 mm/min,
and a sensitivity factor of 20% were adopted. All testings
were done according to the procedure outlined in ASTM
test method D-638.
Dynamic Mechanical and Thermal Analysis
A Dynamic Mechanical and Thermal Analysis (DMTA)
instrument (model IV) from Rheometric Scientic, Piscataway, NJ was used to study the effect of crosslinking and
phase separation on the thermal properties of starchEnPol
blends. A temperature sweep test was conducted with a
temperature range of 30 85C, a frequency of 1 Hz, soak
time of 10 sec, and a xed strain of 0.1%. The extruded
DOI 10.1002/pen
pus BH-2 model and a lens of the type Splan 10PL were
used. A scale of 10 m was adopted for all the samples. The
blends were pressed into lms of thickness of 10 m using
a sample press device. The thin sections were stained with
iodine/KI solution before obtaining images under the microscope at a magnication of 10. This method was used
to differentiate starch from EnPol in the optical micrographs.
CROSSLINKING MECHANISM
Before examining the studys main results, it is instructive to discuss hypothesized reaction mechanism. The proposed crosslinking mechanism for our starch-polyester system is described by the scheme below.
Consider the structure of EnPol.
Initiation
Step 1.
Formation of EnPol microradical
(2)
Step 3.
The EnPol microradical undergoes -scission under high temperature conditions (150C).
(3)
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251
Step 4.
ROO could further react with {2} to form another microradical.
(4)
Propagation
Step 5.
The free radical associated chain attaches itself to MA (double-bond cleavage)
(5)
Step 6.
Microradical {3} formed in step 4 could participate in the grafting process, resulting in the formation of a stable complex
shown below.
(6)
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DOI 10.1002/pen
Step 7.
During stage 2 of extrusion where starch is compounded with MA-grafted EnPol, C-6 atom of starch [12] reacts with the
anhydride group of MA to form starchMApolyester complex.
(7)
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253
(8)
Termination
Step 8.
The reaction could be terminated in two ways; combination (coupling) or disproportionation. The possible termination
steps are given below.
Scheme 1(a) of Coupling
(9)
Scheme 1(b) of Coupling:
(10)
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DOI 10.1002/pen
(11)
Scheme 2(b) of Disproportionation:
(12)
It has been found that polystyrene terminates predominantly by combination, whereas poly(methyl methacrylate)
terminates by disproportionation at polymerization temperatures higher than 60C, and partly by each mechanism at
lower temperatures [22]. Major studies on termination reaction schemes have been completed with linear-chain polymers, but no published research is available on the termination mechanism of starchpolyester crosslinking.
RESULTS AND DISCUSSION
Twin Screw Extrusion
The twin-screw extruder here was used as a reactive
extruder to combine peroxide-initiated grafting reaction and
conventional extrusion into a single process. The screw
conguration, torque, rotational speed, and mass ow rate
are the important terms in determining Specic Mechanical
Energy (SME), which is given as
SME Md/m.
(13)
TABLE 3.
BLEND
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
40S,
SME (kJ/kg)
60PEst
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
0.5MA
0.5MA, 0.3DCP
0.5MA, 0.5DCP
0.5MA, 0.8DCP
0.5MA, 1.2DCP
1MA
1MA, 0.3DCP
1MA, 0.5DCP
1MA, 0.8DCP
1MA, 1.2DCP
1.5MA
1.5MA, 0.3DCP
1.5MA, 0.5DCP
1.5MA, 0.8DCP
1.5MA, 1.2DCP
152.98
198.53
535.23
560.42
579.31
540.81
214.35
271.66
353.23
413.23
598.97
348.94
453.37
454.46
452.53
458.9
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TABLE 4.
Blend
40S, 60PEst
40S, 60PEst, 0.5MA, 0DCP
40S, 60PEst, 0.5MA, 0.3DCP
40S, 60PEst, 0.5MA, 0.5DCP
40S, 60PEst, 0.5MA, 0.8DCP
40S, 60PEst, 0.5MA, 1.2DCP
40S, 60PEst, 1MA
40S, 60PEst, 1MA, 0.3DCP
40S, 60PEst, 1MA, 0.5DCP
40S, 60PEst, 1MA, 0.8DCP
40S, 60PEst, 1MA, 1.2DCP
40S, 60PEst, 1.5MA
40S,60PEst, 1.5MA, 0.3DCP
40S, 60PEst, 1.5MA, 0.5DCP
40S, 60PEst, 1.5MA, 0.8DCP
40S, 60PEst, 1.5MA, 1.2DCP
14.68 0.95
15.70 1.22
20.11 0.9
19.89 1.78
18.63 1.75
17.55 1.55
12.54 4.42
10.5 3.33
15.71 0.96
18.92 1.04
16.05 1.71
17.61 0.54
19.8 2.78
18.27 1.56
19.35 1.61
18.98 1.58
78.68 9.58
80.82 4.38
75.18 8.74
78.68 11.52
92.38 8.65
50.24 10.19
31.06 2.42
150.12 15.15
111.24 12.98
257.35 37.69
165.73 38.61
35.34 3.62
40.86 4.81
36.06 5.51
44.08 7.85
43.02 4.96
36.77 6.02
38.57 12.48
86.87 13.22
79.87 1.10
62.87 15.55
48.38 19.83
51.74 21.79
30.88 9.94
43.07 9.09
51.59 6.89
44.07 5.88
82.64 20.33
88.31 11.63
80.86 5.18
74.78 27.36
79.99 20.28
FIG. 1.
observed that at higher temperatures (80C), blends containing higher compositions of DCP lost their stiffness more
quickly than the blends containing lower compositions of
DCP. For the blend (40S, 60PEst, 0.5MA, 0.3DCP), two
distinct peaks were observed at 55 and 68C. The rst peak
at 55C is due to the addition of the interface modier
(compatibilizer). The other peak at 68C could be due to the
molecular motions within the starch phase. At higher concentrations of DCP, these peaks were found to disappear.
When compared with the transition peak in the uncompatibilized blend, it is found that with the addition of compatibilizer the transition peak in compatibilized blends shifted
towards higher temperatures. It can be observed from Figure
3 that in all the blends containing 1% MA, a drastic decrease
in storage modulus (E) is observed. This indicates that as
the concentration of MA in the blend is increased from 0.5
to 1%, there is a sharp decrease in stiffness. This is in
agreement with the tensile testing results. In all the blends
containing 1% MA, a transition peak is observed between
70C and 85C, which is a shift by about 10C when
compared with the transition peak in the blend (40S,
60PEst, 0.5MA, 0.3DCP). This indicates that the
POLYMER ENGINEERING AND SCIENCE2006
257
crosslinked points could have been obstructing the conformational mobility of the segments of EnPol, resulting in
further shift of the transition peak. A series of transitions
observed in the blends containing 0.3, 0.5, and 0.8% DCP
could be due to the side groups and segmental motions of
the crosslinked chains.
It is noticeable that all the blends containing 1.5% MA
have storage modulus between that of blends containing 1
and 0.5% MA. These blends are found to exhibit similar
tensile properties to the blends containing 0.5% MA. Most
of these blends exhibit a transition between 50 and 60C,
which could again be due to the presence of interface
modier. These blends also showed transition peak between
60 and 70C, signifying the molecular motion within starch.
X-ray Photoelectron Spectroscopy
Although X-ray Photoelectron Spectroscopy (XPS) is a
surface analysis technique, it still gives information about
the structure of crosslinked polymers. Compression molded
lms of six blends [(40S, 60PEst), (40S, 60PEst, 0.5MA,
0.5DCP), (40S, 60PEst, 1MA), (40S, 60PEst, 1MA,
0.8DCP), (40S, 60PEst, 1.5MA), (40S, 60PEst, 1.5MA,
258
FIG. 5. High resolution scans of (a) uncompatibilized blend; (b) 40S, 60PEst, 0.5MA, 0.5DCP; (c) 40S,
60PEst, 1MA; (d) 40S, 60PEst, 1MA, 0.8DCP; (e) 40S, 60PEst, 1.5MA; (f) 40S, 60PEst, 1.5MA, 0.5DCP.
TABLE 5.
Blend
40S,
40S,
40S,
40S,
40S,
40S,
60PEst
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
0.5MA, 0.5DCP
1MA
1MA, 0.8DCP
1.5MA
1.5MA, 0.8DCP
DOI 10.1002/pen
here that XPS does not detect H. It was observed that the
composition of OCOO groups in the blend (40S, 60PEst,
1MA, 0.8DCP) was higher than the composition of OCOO
groups in other blends. The OCOO peak in the curve-tted
graph is due to the presence of OCOO groups of EnPol and
OCOOH groups, which are formed due to crosslinking
(refer to mechanism). As crosslinking increases, the percentage of OCOOH groups in the compatibilized blends
A1/A2
983
880
1246
1362
872
789
1372
1074
1508
1125
1354
977
0.72
0.82
0.83
1.21
0.64
0.81
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60PEst
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
60PEst,
0.5MA, 0.3DCP
0.5MA, 0.5DCP
0.5MA, 0.8DCP
0.5MA, 1.2DCP
1MA
1MA, 0.3DCP
1MA, 0.5DCP
1MA, 0.8DCP
1MA, 1.2DCP
1.5MA
1.5MA, 0.3DCP
1.5MA, 0.5DCP
1.5MA, 0.8DCP
1.5MA, 1.2DCP
Endotherm T (C)
Exotherm T (C)
98.8
99.1
98.4
98.4
97.1
99.9
98.5
98.2
97.5
97.5
99.0
98.9
98.1
98.1
98.2
63.8
49.6
45.9
51.6
52.6
48.4
50.7
48.4
59.2
64.8
50.2
55.9
45.3
44.8
45.1
ble 6). For compatibilized starchpolyester blends, no signicant change in the endotherm (melting) temperature was
observed, but the exotherm (crystallization) temperatures of
all the compatibilized blends were lower than the crystallization temperature of the base blend (refer to Table 6).
Hence, crosslinking agents do have signicant effect on the
crystallization temperature of starchpolyester blends. Because of -scission of the polyester the chains could form
crosslinked regions, resulting in the restriction of polymer
chain mobility, which could signicantly reduce the degree
of crystallinity. However, it is interesting to note that the
crystallization temperatures of the two blends at 1.0% MA
addition {(40S, 60PEst, 1MA, 0.8DCP) and (40S, 60PEst,
1MA, 1.2DCP)} were higher than the crystallization temperatures of other compatibilized blends. In fact, the greatest increase in exotherm temperature was found in (40S,
60PEst, 1MA, 1.2DCP). The presence of optimum concentration of the compatibilizer could have prevented appreciable micelle formation and hence reduced the interfacial
energy of the blend. As a result, the degree of crystallization
could have increased in both phases and at the interface,
further leading to an increase in the number of nucleation
sites. In the two blends mentioned earlier, the compositions
of MA and DCP could hence be in the proximity of their
respective optimum concentrations. The crystallization temperatures of other compatibilized blends were low, indicating that the compositions of the crosslinking agent and the
initiator in these blends are not optimized. It could also be
observed that the crystallization temperature for the uncompatibilized blend (40S, 60PEst) is quite high (63.8C), and
yet the blend exhibited poor mechanical properties. The
absence of crosslinking agent could promote micelle formation at the interface of the hydrophobic polyester and the
hydrophilic starch, thus contributing towards poor mechanical properties. At the same time, the two phases could
crystallize in their domains, resulting in an increase in the
crystallization temperature of the blend.
Optical Microscopy
The optical micrographs of the uncompatibilized blend
and blends that did not contain DCP are shown in Figure 6.
FIG. 6. Optical micrographs of (a) uncompatibilized blend; (b) 40S, 60PEst, 1MA ; and (c) 40S, 60PEst,
1.5MA.
260
DOI 10.1002/pen
FIG. 8. Optical micrographs of (a) 40S, 60PEst, 1MA, 0.3DCP; (b) 40S,
60PEst, 1MA, 0.5DCP; (c) 40S, 60PEst, 1MA, 0.8DCP; and (d) 40S,
60PEst, 1MA, 1.2DCP.
261
All blends (0.5, 1.0, and 1.5 wt% MA) showed an improvement in Youngs modulus and stress at break.
Blends with 1.0% MA showed larger improvements in
elongation at break.
DMTA studies revealed that the blends containing 1%
MA had lower stiffness (E) than blends containing 0.5%
MA and 1.5% MA.
XPS analysis indicated the presence of more OCOO
groups in the blend with 1% MA, thus supporting the
proposed compatibilized structure for the blend.
The DSC results indicated that the crystallization temperatures were reduced with increasing compatibilizers because of an increased hindrance to crystallization. Crystallization temperatures of the two blends at 1.0% MA
addition {(40S, 60PEst, 1MA, 0.8DCP) and (40S, 60PEst,
1MA, 1.2DCP)} had higher than the crystallization temperatures than that of other compatibilized blends.
Optical micrographs of compatibilized blends with 1%
MA revealed uniform distribution of starch in the polymer matrix, indicating compatibilization between starch
and polyester phases
Thus optical, DSC, and XPS tests indicates that a reactively compatibilized structure is optimized for the 1.0%
MA samples. Interestingly the 1.0% MA samples showed
lower elastic modulus or stiffness during DMTA tests, yet
showed high youngs modulus, stress at break and elongation at break during tensile testing. This is possibly due to
the fact the DMTA tests are linear deformation tests and the
tensile tests induce nonlinear deformation. That is, the linear
DMTA tests determine a lower linear elastic modulus under
small deformations, possibly due to the plasticizing addition
of the MA to the system as previously noted [30], and the
MA induced crosslinks have little effect. However, under
nonlinear tensile testing the deformation is larger and more
destructive, and the compatibilized network structure is able
to reduce the breaking of tie layers commonly described in
basic polymer fracture studies. It is also interesting that the
Youngs modulus, stress at break and elongation at break all
increase, unlike normal composite systems, which sacrice
elongation [extensibility] for increases in strength.
REFERENCES
1. R. Chandra and R. Rustgi, Polym. Degrad. Stab., 56, 185
(1997).
2. W.M. Doane, J. Polym. Mater., 11, 229 (1994).
3. S.A. McGlashan and P.J. Halley, Preparation and Characterisation of Biodegradable Starch-Based Nanocomposite Packaging Materials, in Polymer symposium, University of
Queensland (2001).
4. P.J. Frazier, P. Richmond, and A.M. Donald, Starch Structure
and Functionality, Royal Society of Chemistry, Cambrdige,
UK (1997).
5. T. Galliard, Starch: Properties and Potential, Wiley: New
York (1987).
CONCLUSIONS
6. R.F. Tester, J.B. South, W.R. Morrison, and R.P. Ellis, J. Cereal Sci., 13, 113 (1991).
7. R.F. Tester, W.R. Morrison, R.P. Ellis, J.R. Piggott, and G.R.
Batts, J. Cereal Sci., 22, 63 (1995).
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