Macromolecular Research, Vol. 21, No. 7, pp 793-800 (2013) www.springer.

com/13233
DOI 10.1007/s13233-013-1088-4 pISSN 1598-5032 eISSN 2092-7673

Mechanical Performance, Water Absorption Behavior and Biodegradability of

Poly(methyl methacrylate)-Modified Starch/SBR Biocomposites

Mei-Chun Li, Xin Ge, and Ur Ryong Cho*

Department of Applied Chemical Engineering, Korea University of Technology and Education, Chungnam 330-708, Korea

Received June 26, 2012; Revised September 9, 2012; Accepted September 10, 2012

Abstract: Natural corn starch was modified by surface grafting with poly(methyl methacrylate) (PMMA) through
emulsion copolymerization and then compounded with styrene-butadiene rubber (SBR) latex in order to prepare
PMMA-modified starch/SBR biocomposites. The effect of methyl methacrylate (MMA) and starch concentration
on the mechanical properties, morphology, toluene swelling behavior, water absorption behavior and biodegradabil-
ity of PMMA-modified starch/SBR biocomposites was investigated. Results showed that the optimum mechanical
properties were achieved when the concentrations of MMA and starch were 10 and 30 phr, respectively, which could
be also confirmed through the observations from FE-SEM micrographs and equilibrium welling test. Guth-Gold and
Halpin-Tsai models were employed to predict the modulus of PMMA-modified starch/SBR biocomposites. Halpin-
Tsai model was better fitted with the experimentally measured data than Guth-Gold model. The water absorption
ratio of PMMA-modified starch/SBR biocomposites was strongly influenced by the immersion time and the starch
concentration, which further caused a significant effect on the biodegradability of biocomposites.
Keywords: starch, styrene-butadiene rubber (SBR), poly(methyl methacrylate), grafting, interfacial interaction.

Introduction Recently, the development of starch as reinforcing filler in

As the surge in the oil price and global warming occurring
from carbon dioxide emissions, the application of natural
resources in the polymer matrix has attracted enormous
interest from both academic and industrial researchers in
recent years. The application of renewable resources instead
of non-renewable resources in the polymer matrix not only
largely reduces the cost of products, but also is good for our
environment. Among lots of the renewable resources, starch
is one of the cheapest and most abundant natural resources
on the earth, which can be derived from corn, wheat, potato
and rice etc. Therefore, starch has been widely investigated
for the potential application in various fields, such as coat-
ing,1 adhesives,2,3 flocculants,4-6 superabsorbent polymers,7,8
biodegradable polymers9 and packaging films.10 For exam-
ple, Imam et al.2,3 developed an environmentally friendly
wood adhesive by crosslinking corn starch and poly(vinyl
alcohol) with hexamethoxymethylmelamide. Sen et al.4 syn-
thesized a novel flocculant based on poly(acrylamide) grafted
carboxymethyl starch. Wu et al.7,8 prepared starch-based
superabsorbent by reaction among potato starch, acrylamide
and mineral ultrafine powder. Avella et al.10 developed a
novel food packaging films by blending of starch and nano-
clay.
*Corresponding Author. E-mail: urcho@kut.ac.kr
the rubber compounds has received increasing attention.11-18
It is well known that the hydrophilic surface of starch pre-
vents adhesions with hydrophobic rubber matrix, thus the
wide use of natural starch as reinforcing filler in the rubber
compounds is limited. One of the common methods to over-
come this disadvantage is to modify the surface characteris-
tic of reinforcing fillers via chemical grafting of polymers.
The grafting polymers are expected to not only enhance the
interfacial adhesion between two incompatible phases, but
also to avoid the nano-particle aggregations or micro-particle
agglomerates, and consequently result in the superior rein-
forcement. Among lots of grafting polymers, poly(methyl
methacrylate) (PMMA) has been extensively used for sur-
face modification of various organic or inorganic fillers, such
as starch,19-21 cellulose,22,23 nanoclay,24 mesoporous MCM-41,25
silica,26,27 carbon nanotubes,28,29 halloysite nanotubes,30 graph-
ite oxide,31 magnetite nano-particles,32 and nano antimony
trioxide,33 since PMMA is non-toxic and very cheap. For
example, zhu et al.26 modified silica by surface grafting of
PMMA and then mixed with poly(vinyl chloride) (PVC) to
prepare PMMA-modified silica/PVC nanocomposites. They
found that PMMA grafts improved significantly the disper-
sion of silica and endowed the compatibility between silica
and PVC, resulting in better mechanical performances. Simi-
larly, the significant improvement in mechanical perfor-
mances of PVC composites was also achieved by the

The Polymer Society of Korea 793

 M.-C. Li et al.
addition of PMMA-modified cellulose fibers,23 PMMA-modi-
fied halloysite nanotubes,30 and PMMA-modified nano anti-
mony trioxide.33 Wang et al.28 used PMMA-modified
multiwalled carbon nanotubes (MWNTs) to reinforce
poly(styrene-co-acrylonitrile) matrix. They observed that
the introduction of PMMA-modified MWNTs led to
increases in the overall mechanical properties, in which the
Young’s modulus, tensile strength, and toughness were
increased by 90%, 51%, and 614%, respectively. It confirms
that PMMA grafts effectively act as “bridges”, which link the
fillers with the surrounding polymer matrix via physical
entanglements.
In our previous study,34 we reported the emulsion modifi-
cation and latex compounding method to prepare high perfor-
mances modified starch/SBR biocomposites. The remarkable
improvement in tensile strength was observed by the addition
of modified starch. In particular, PMMA-modified starch/
SBR biocomposites showed much superior mechanical per-
formances than PBA or PS-modified starch/SBR biocompos-
ites. In this study, we mainly investigated the effect of MMA
and starch concentration on the various properties, such as
mechanical performance, morphology, toluene swelling behav-
ior, water absorption behavior and biodegradability of the
PMMA-modified starch/SBR biocomposites.
Experimental
Materials. SBR 1502 (styrene content 23.5%) was kindly
provided from Korea KumHo Petrochemical Company
(KKPC). Corn starch (branched amylopectin 75%, linear
amylose 25%) was kindly supplied by Samyang Genex
Company, South Korea. MMA monomer was purchased
from Dae Jung Chemical and metal co., Ltd, South Korea.
Initiator potassium persulfate (KPS) were purchased from
DukSan Pharmaceutical Co., Ltd. Emulsifier dodecylbeze-
nesulfonic acid sodium salt (DBS-Na) was purchased from
JunSei Chemical Co., Ltd. All the chemicals were used as
received without further purification.
Preparation of PMMA-Modified Starch through Emul-
sion Polymerization. A certain amount of starch (10, 20,
30, 40, and 50 phr) were first dispersed in excess deionized
water. Subsequently, the starch suspension was continuously
stirred at 80 oC in a water bath under nitrogen atmosphere.
The gelatinized starch was obtained until the suspension
became transparent. PMMA-modified starch was synthe-
sized by conventional emulsion polymerization using DBS-Na
as an emulsifier as reported previously.34 A certain amount
of MMA monomers (2.5, 5, 7.5, 10, and 12.5 phr) were added
into the pre-prepared DBS-Na solution with strongly
mechanical stirring. After 30 min pre-emulsifying, the MMA
monomer emulsion was slowly added into the starch paste.
Finally, the graft copolymerization was initiated by the addi-
tion of KPS solution. The graft copolymerization was car-
ried out under nitrogen atmosphere at 80 oC for 3 h. The
794
grafting percentages of PMMA grafts and their molecular
weights in the PMMA-modified starch copolymers were
measured as reported previously.34
Compounding. PMMA-modified starch emulsion and
SBR latex were directly mixed in a large container with vig-
orously mechanical stirring for 30 min at room temperature
to make a well dispersion of PMMA-modified starch parti-
cles in the SBR matrix. And then the mixtures were dried in
an oven at 70 oC until the weight kept constantly. Com-
pounding was carried out on a two-roll mixing mill. The
obtained biocomposites were compounded with the follow-
ing rubber additives: zinc oxide (3 phr), stearic acid (1 phr),
antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer
(1 phr), sulfur (2 phr), accelerator n-cyclohexyl-2-benzothi-
azole sulfenamide (2 phr), and accelerator dibenzothiazole
disulfide (0.5 phr). Finally, the biocomposites were vulca-
nized under 10 MPa for t90 at 150 oC in a hot-pressing machine.
The thickness of the specimens was about 2 mm.
Characterization. The PMMA-modified starch/SBR bio-
composites were characterized by using tension test, field
emission scanning electron microscopy (FE-SEM) observa-
tion, swelling test (including toluene swelling test and water
swelling test) and soil burial test.
Tension test was conducted on a Tinius Oisen H5KT-0401
testing machine at a speed of 500 mm/min according to
ASTM D412. The specimens used for tension test was
dumbbell-shape with dimensions 25 mm×6 mm×2 mm.
The tensile fracture surfaces of biocomposites were exam-
ined using a JSM-7500 Field Emission Scanning Electron
Microscopy (FE-SEM, JEOL). The specimens were coated
with a thin layer of gold before observation.
Toluene swelling test was carried out in toluene for 24 h
according to ASTM D471-79. Based on the toluene swell-
ing test, some useful parameters, such as swelling ratio (Q),
the molecular weight between crosslinks (Mc), and the
degree of crosslinking density (vc), could be obtained. The
swelling ratio (Q) was calculated by using equation:
( W – W0 ) ⁄ ρs
Q = ---------------------------- × 100% (1)
W ⁄ ρr
Where W is the weight of swollen rubber compounds, W0 is
the original weight of rubber compounds, ρr is the density
of rubber (ρSBR=0.933 g/cm3), and ρs is the density of sol-
vent (ρtoluene=0.867 g/cm3).
Equilibrium swelling could be applied to determine the
degree of crosslinking density (vc), too. According to the
theory of Flory-Rehner,35 the molecular weight between
crosslinks (Mc) was a function of the volume fraction of
rubber in the swollen rubber compounds (Vr), which could
be written as following:
1---
3 V
–ρr V1 ⎛ Vr – -----r⎞
⎝ 2⎠
Mc = ----------------------------------------------2 (2)
ln ( 1 – Vr ) + Vr + xVr
Macromol. Res., Vol. 21, No. 7, 2013
 Mechanical Performance, Water Absorption, and Biodegradability of PMMA-Modified Starch/SBR Biocomposites
Where V1 is the molar volume of the solvent (Vtoluene=106.35
cm3/mol) and x is the Flory-Huggins polymer solvent inter-
action parameter. For SBR/toluene system, x=0.446.
The volume fraction of SBR rubber in the swollen rubber
compounds (Vr) was calculated by the equation:
( W – FW0 ) ⁄ ρr
Vr = --------------------------------------------------
- (3)
( W – FW0 ) ⁄ ρr + A0 ⁄ ρ s
Where F is the weight fraction of insoluble components in
the rubber compounds, A0 is the weight of absorbed solvent.
Finally, the degree of crosslinking density (vc) was given
by the equation:
1
vc = ------ (4)
Mc
Water absorption test was carried out in deionized water
according to ASTM D-570. Before immersion, the speci-
mens were dried in an oven for about 2 h at 80 oC. After
cooling to room temperature, the specimens were carefully
weighed. And then the specimens were immersed into
deionized water in bottles at room temperature. The weight
increase was periodically measured. The water absorption
ratio (Mt) as a function of time t was calculated by the fol-
lowing equation:
wt – w0
Mt = --------------- × 100% (5)
w0
Where wt is the weight of specimen at time t, w0 is the initial
weight of specimen.
Biodegradation of all the biocomposites was investigated
using the soil burial method as reported by Chandra et al.36
The specimens with dimensions 10 mm×6 mm×2 mm were
directly buried in the soil at the depth of 10 cm in a farm-
land close to Korea University of Technology and Educa-
tion in Cheonan City, South Korea. The moisture depended
on the weather and the surrounding environment. The soil
burial test was carried out for 3 months (from May 1st, 2012
to August 1st 2012). The weight loss was calculated before
and after biodegradation.
Results and Discussion
Mechanical Properties. Owing to the incompatibility
between hydrophilic starch and hydrophobic SBR matrix,
Table I. Effect of Molecular Weight of PMMA Grafts on the Mechanical Properties of PMMA-Modified Starch/SBR Biocomposites
MMA Concentration (phr) 0 2.5
Grafting Percentage (%) 0 5.7
5
Molecular Weight×10 (g/mol) 0 0.23
300% Modulus (MPa) 2.1
Tensile Strength (MPa) 3.3
Elongation at Break (%) 564
Macromol. Res., Vol. 21, No. 7, 2013
the incorporation of starch always deteriorated the mechani-
cal performances of rubber compounds rather than reinforc-
ing. Thus, to obtain the high mechanical performances of
starch/SBR biocomposites, starch was modified by surface
grafting of PMMA. PMMA grafts in the PMMA-modified
starch were designed to avoid the starch particles from
agglomerates and to form some physical entanglements
with SBR macromolecular chains. In addition, we believed
that if the physical entanglements indeed existed, the molec-
ular weight of PMMA grafts played a key role on the physical
entanglements between these two phases. More specifically,
PMMA grafts with higher molecular weight had a greater
chance to entangle with rubber chains, resulting in higher
values in the strength of physical entanglement. Therefore,
the effect of the molecular weight of PMMA grafts on the
mechanical properties of PMMA-modified starch/SBR bio-
composites (with a fixed starch concentration as 20 phr)
was investigated to confirm the existence of physical entan-
glements in the biocomposites, as presented in Table I. It
can be observed that as the molecular weight increased from
0.23×105 to 1.4×105 g/mol, the 300% modulus was gradu-
ally increased from 1.9 to 3.2 MPa, which strongly con-
firmed our assumption that the physical entanglements
existed between PMMA grafts and SBR macromolecular
chains. Besides, in the present PMMA-modified starch/
SBR system, due to the presence of many electronegative
atoms, Van Der Waals type of bonding could be formed via
the electrostatic attractions. This formed Van Der Waals
type of bonding was also supposed to enhance the interfa-
cial adhesion. The tensile strength and elongation at break
of starch/SBR biocomposites were found to be simulta-
neously improved by the introduction of PMMA grafts on
the starch surfaces. For example, the introduction of only
2.5 phr of MMA caused 54% increase in the tensile strength
and 57% increase in the elongation at break. The developed
elongation at break could be attributed to the entanglements
slippage occurred between PMMA grafts and SBR macromo-
lecular chains.37 Especially, when specimens were stretched at
large strain, the slippage processes (including sliding-in or
sliding-out) vigorously took place in the entanglement net-
works, which allowed the specimens to be broken at a rela-
tive higher extension. The optimal mechanical performances
were achieved when the MMA concentration was 10 phr, in
which the tensile strength, 300% modulus and elongation at
5 7.5 10 12.5
10.7 18.2 30.8 41.3
0.28 0.35 0.46 1.4
1.9 2.2 2.3 2.7 3.2
5.1 5.9 7.8 9.7 9.4
888 876 1,021 940 920
795
 M.-C. Li et al.

break were increased by 194%, 28%, 67%, respectively, filler-filler interaction was more prominent than the filler-
compared with starch/SBR biocomposites. Further increased polymer interfacial interaction in the biocomposites, and
the MMA concentration had a negative effect both on the consequently deteriorated the mechanical performances.
tensile strength and elongation at break. Based on the results of mechanical analysis, it concluded
The effect of starch concentration on the mechanical per- that 30 phr could be considered as optimal concentration for
formances of PMMA-modified starch/SBR biocomposites the development on the mechanical properties PMMA-
(with a fixed MMA concentration as 10 phr) was also inves- modified starch/SBR biocomposites.
tigated, as shown in Figure 1. The incorporation of PMMA- The modulus of filler/polymer composites was governed
modified starch had a positive effect on the overall mechan- by some parameters, such as the intrinsic properties of poly-
ical properties of SBR compounds, which could be attrib- mer (crystalline or amorphous), the intrinsic properties of
uted to the well dispersion of PMMA-modified starch particles fillers (particle size, surface characteristics and aspect ratio),
as well as the occurred interfacial adhesion between PMMA- the filler content and the filler-polymer interfacial interac-
modified starch particles and SBR matrix resulted from tion. Owing to the much higher modulus of filler compared
physical entanglements. A compatible interface could trans- with polymer, the incorporation of rigid filler increased sig-
fer more stress from polymer matrix to fillers, resulting in nificantly the modulus of filler/polymer composites. The
the better mechanical properties.26 The optimal mechanical modulus of filler/polymer composites could be predicted by
properties were achieved when starch concentration was 30 using modified Guth-Gold model and Halpin-Tsai model.
phr, in which the tensile strength, 300% modulus, and elon- For modified Guth-Gold model,38 the Young’s modulus E of
gation at break were increased by 272%, 217%, and 34%, filler-polymer composites could be calculated using eq. (6).
respectively, compared with neat SBR. Addition of excess
starch, such as 40 and 50 phr, led to reduction both in the
tensile strength and elongation at break. Two reasons may
be responsible. First, it is well known that particle size, dis-
persion state and interfacial interaction are three crucial
parameters for the development on mechanical properties of
filler/polymer composites. Or in other word, the optimum
mechanical properties are resulted from the synergistic
effect of particle size, dispersion state and interfacial inter-
action. When the concentration of starch exceeded 30 phr,
although the physical entanglement was stronger, the dis-
persion state of starch became worse with starch aggrega-
tions (to be verified in morphology part). If the latter one was
dominant, the mechanical properties would be decreased.
Second, when the starch concentration exceeded 30 phr, the

Figure 2. Experimentally measured modulus and theoretically

Figure 1. Mechanical properties of PMMA-modified starch/ predicted modulus by using (a) modified Guth-Gold model and
SBR biocomposites: effect of starch concentration. (b) Halpin-Tsai model.

796 Macromol. Res., Vol. 21, No. 7, 2013

 Mechanical Performance, Water Absorption, and Biodegradability of PMMA-Modified Starch/SBR Biocomposites

E = E0 ( 1 + 0.67f ϕ + 1.62f ϕ )
2 2
(6)

Where E0 is the Young’s modulus of unfilled rubber, ϕ is the

volume fraction of filler in the compounds, and f is the
shape factor of the particles or agglomerates. For Halpin-
Tsai model,39 the Young’s modulus E of filler-polymer com-
pounds could be calculated using eqs. (7) and (8).
1 + 2f εϕ
E = E0 ⎛⎝ -------------------⎞⎠ (7)
1 – εϕ

(E ⁄ E ) – 1
ε = --------------------------
f 0
- (8)
( Ef ⁄ E0 ) + 2f
Where E0 is the Young’s modulus of unfilled rubber, ϕ is the
volume fraction of filler in the compounds; f is the shape
factor of the particles or agglomerates, Ef is the Young’s modu-
lus of filler. In the case of corn starch, the Ef was reported to
be approximately 15 GPa.40 Figure 2 shows the comparation
between the experimentally measured 300% modulus and
theoretically predicted modulus by using (a) modified Guth- Figure 3. FE-SEM micrographs of tensile fracture surfaces of
Gold model and (b) Halpin-Tsai model. In the case of Guth- PMMA-modified starch/SBR biocomposites: (a) MMA 0 phr, (b)
Gold model, the theoretically predicted values were closed MMA 5 phr, (c) MMA 10 phr, (d) MMA 12.5 phr; Scale bar: 10 µm.
to the experimentally measured values as the shape factor f
was applied as 5. In the case of Halpin-Tsai model, the theo-
retically predicted values were closed to the experimentally
measured values as the shape factor f was applied as 4. Com-
pared with modified Guth-Gold model, the Halpin-Tsai
model was better fitted with the experimentally measured
results.
Morphology. The dispersion state of PMMA-modified
starch in the SBR matrix was observed using FE-SEM. Fig-
ure 3 shows the effect of MMA concentration on the tensile
fracture surface of PMMA-modified starch/SBR biocom-
posites. In the case of starch/SBR biocomposites (MMA 0
phr) as shown in Figure 3(a), although the starch was treated
by gelatinization, compounding and hot pressing, the parti-
cle size of starch was still large (1-15 µm) due to its strong
re-crystallization and re-gathering characteristics resulting
from the inter-molecular hydrogen bonding formed by the
hydroxyl groups on the starch granule surface.16 In the case
of PMMA-modified starch/SBR biocomposites as shown in
Figure 3(b), (c), and (d), the very clear tensile fracture sur-
face could be observed, suggesting the uniform dispersion
of PMMA-modified starch in the SBR matrix. For example, Figure 4. FE-SEM micrographs of tensile fracture surfaces of
the introduction of only 5 phr MMA led to a significant PMMA-modified starch/SBR biocomposites: (a) starch 0 phr, (b)
reduction in the particle size of starch. This observation starch 10 phr, (c) starch 30 phr, (d) starch 50 phr; Scale bar: 10 µm.
strongly proved our design that PMMA grafts effectively
avoided the starch particles from agglomerates. Additionally, it
can be seen that as the MMA concentration increased, the sile fracture surface of PMMA-modified starch/SBR bio-
rougher the facture surface became. It suggested that the composites. One can see that the starch agglomerates gradually
strength of physical entanglements was gradually enhanced appeared on the fracture surface as the starch concentration
as the MMA concentration increased, which well corre- increased. For example, when starch concentration was 50
sponded with the observed trend of mechanical properties. phr, a large amount of starch agglomerates with particle size
Figure 4 shows the effect of starch concentration on the ten- approximately 1-10 µm were observed on the surface, as

Macromol. Res., Vol. 21, No. 7, 2013 797

 M.-C. Li et al.

Table II. Swelling Characteristics of PMMA-Modified Starch/SBR Biocomposites

Starch Concentration (phr) 0 10 20 30 40 50
Q (%) 358.45 356.57 270.48 226.29 196.52 179.55
Mc (g/mol) 489.75 482.58 465.17 460.71 462.79 475.47
vc×10 (mol/g)
-3
2.04 2.07 2.15 2.17 2.16 2.10

shown in Figure 4(d). These generated agglomerates were

responsible for the deteriorated mechanical properties of
PMMA-modified starch/SBR biocomposites with high starch
concentrations.
Toluene Swelling Behavior. Toluene swelling test is a
useful tool to investigate the physicochemical properties of
filler/polymer composites. Through toluene swelling test,
various swelling characteristics, such as swelling ratio (Q),
the molecular weight between crosslinks (Mc) and the
degree of crosslinking density (vc), could be obtained, as
listed in Table II. As the starch concentration increased from
0 to 50 phr, the swelling ratio (Q) was significantly decreased
from 358.45% to 179.55%. The formed interfacial interac-
tion via physical entanglements between PMMA-modified
starch and SBR matrix could restrict the penetration of sol-
vent molecules into the bulk of SBR. The degree of crosslinking
density (vc) was found to be slightly increased from 2.04×10-3
to 2.17×10-3 mol/g, as the starch concentration increased
from 0 to 30 phr. Owing to the contribution of physical
crosslinking, the increase in crosslinking density was not
significant. Further addition of starch from 30 to 50 phr led
to the decrease in the crosslinking density value from
2.17×10-3 to 2.10×10-3mol/g, which might be ascribed to the
poor dispersion of fillers in the SBR matrix.
Water Absorption Behavior. Starch is highly hydro-
philic in nature due to its large number of hydroxyl groups
on the backbones. One of major bottlenecks for the applica-
tion of starch-based products is its great water absorption
characteristic. More specifically, the high moisture absorp-
tion of starch deteriorates the adhesion with polymeric
matrix and then lead to premature ageing by decomposition
and loss of strength. Therefore, it is very essential to investi-
gate the water absorption properties of PMMA-modified
starch/SBR biocomposites. Figure 5 shows the effect of
immersion time t and starch concentration on the water
absorption ratio of PMMA-modified starch/SBR biocom-
posites. It has been reported that the water absorption was
strongly dependent on various factors, such as the immer-
sion time, filler concentration, interfacial adhesion and the
number of voids formed in the interfacial area.42-44 As
expected, a significant increase in the water absorption of
SBR compounds was observed with the addition of PMMA-
modified starch. For example, when the biocomposites were
immersed into water for only 1 h, the water absorption ratio
was increased up to 0.88%, 1.03%, 1.08%, 1.78%, and
2.59% for the biocomposites with 10, 20, 30, 40, and 50 phr
Figure 5. Water absorption of PMMA-modified starch/SBR bio-
composites: effect of starch concentration and water immersion time.
of starch, respectively. Additionally, it can be also seen that
the water absorption ratio was also increased as the immer-
sion time increased. These observations agreed with litera-
ture,41-43 in which the moisture uptake of starch-based bio-
composites was also increased with the immersion time and
the starch concentration increased. Danjaji et al.41 suggested
that the exposed starch particles would absorb water faster
than those in the interior. Bikiaris and Panayiotou43 deduced
that the significant increase in water absorption was attrib-
uted to the poor interfacial adhesion and the increased diffi-
culty in the polymer chain arrangements. In this study, when
the biocomposites were immersed in the water for 1008 h,
the highest water absorption ratio was obtained to be 14.2%,
22.9%, 24.7%, 26.9%, 28.4%, and 31.1% for the biocom-
posites with 10, 20, 30, 40, and 50 phr of starch, respec-
tively, which was much higher than that of LDPE/starch,36
MA-g-LLDPE/starch41 and PCL/starch blends.42 Therefore,
the relative high water absorption property of PMMA-mod-
ified starch/SBR biocomposites could be a severe handicap
for application them out of door.
Biodegradability. The biodegradability of PMMA-modi-
fied starch/SBR biocomposites was investigated by soil
burial test for 3 months. Figure 6 shows the effect of starch
concentration and soil burial time on the weight loss of the
biocomposites. Similarly, it can be seen that the loss weight

798 Macromol. Res., Vol. 21, No. 7, 2013

 Mechanical Performance, Water Absorption, and Biodegradability of PMMA-Modified Starch/SBR Biocomposites
Figure 6. Weight loss of PMMA-modified starch/SBR biocom-
posites: effect of starch concentration and soil burial time.
was also increased as the starch concentration and the soil
buried time increased. It has been reported that the biode-
gradability of biocomposites was correlated with its ability
of moisture absorption in the soil.42 The increase in the
water absorption could be responsible for the observed trend
in the biodegradability. Additionally, a dramatic increase in
the weight loss could be observed when starch concentra-
Figure 7. Surface morphology of PMMA-modified starch/SBR
biocomposites: before and after soil burial treatment.
Macromol. Res., Vol. 21, No. 7, 2013
tion exceeded 30 phr, which might be attributed to the
reduction in the crosslinking density of biocomposites. It is
believed that when the biocomposites were buried in the
soil, microorganisms preferably attacked the specimens
which had higher moisture contents and lower crosslinking
density, resulting in higher weight loss. The surface mor-
phologies of biocomposites (starch concentration 0, 10, 30
and 50 phr) with 0, 28, and 90 days of soil burial treatment
are shown in Figure 7. After the soil burial treatment, a large
number of perforations were observed on the surface of bio-
composites, which was due to the removal of starch particles
by soil microorganisms. Apparently, the number of perfora-
tions was increased as the starch concentration and the soil
buried time increased, which was consistent with their weight
loss results.
Conclusions
PMMA-modified starch was used as reinforcing filler in
the SBR matrix. Owing to the improved dispersion and the
occurrence of physical entanglements between PMMA
grafts and SBR macromolecular chains, the incorporation of
PMMA-modified starch increased the overall mechanical
properties of SBR compounds. We found that when the con-
centration of MMA and starch was 10 and 30 phr, respec-
tively; the optimal mechanical properties could be achieved.
We also investigated the effect of starch concentration on
the crosslinking density, water absorption ratio and biode-
gradability of PMMA-modified starch/SBR biocomposites.
The results indicated that when the starch concentration was
less than 30 phr, the biocomposites exhibited high crosslink-
ing density, relative low water absorption ratio and low bio-
degradability. Further incorporation of starch (40 or 50 phr)
easily formed agglomerates and therefore decreased the
crosslinking density of biocomposites, while dramatically
increased the water absorption ratio and biodegradability of
biocomoposites.
Acknowledgment. This research was financially supported
by the Ministry of Education, Science Technology (MEST)
and National Research Foundation of Korea (NRF) through
the Human Resource Training Project for Regional Innova-
tion.
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