360 Full Paper

Summary: Attempts were made to prepare thermoplastic

elastomers (TPE) from scrap rubber powder (SRP) and linear
low-density polyethylene (LLDPE) as thermoplastic poly-
mer matrix. The solid-phase grafted copolymer of LLDPE
(LLDPE-g-VM) and epoxidized natural rubber (ENR) were
used as dual compatibilizers to improve the interfacial adhe-
sion between SRP and LLDPE. The compatibilized SRP/
LLDPE blends had obviously improved the interfacial pro-
perties between SRP particles and LLDPE. Using this
method, thermoplastic elastomer was prepared successfully.
The mechanical properties especially elongation at break was
improved significantly. SEM and TEM studies showed that
the ENR/LLDPE-g-VM dual compatibilizer improved the
distribution state of SRP particles in LLDPE and the adhesion
between SRP and LLDPE. DSC results showed a distinct
glass transition at 74 8C of the interfacial region. The impro-
vement in mechanical properties was attributed to the
enhanced interfacial properties of the blend.

Surface of SRP particles of the composites compatibilized by

the dual compatibilizer.

Thermoplastic Elastomers Derived from Scrap Rubber

Powder/LLDPE Blend with LLDPE-graft-(Epoxidized
Natural Rubber) Dual Compatibilizer
Baochun Guo,* Yan Cao, Demin Jia, Qinghua Qiu
Department of Polymer Materials and Engineering, South China University of Technology, Guangzhou 510640, China
Fax: 8620-38672016; E-mail: psbcguo@scut.edu.cn

Received: October 16, 2003; Revised: December 24, 2003; Accepted: January 5, 2004; DOI: 10.1002/mame.200300311
Keywords: scrap rubber powder; linear low-density polyethylene; thermoplastic elastomer; compatibilization

Introduction combustion for fuel, landfills, incorporating in the

The boom in the automobile industry has fueled rapid
development of the tire industry. A consequence of this
development is the so-called black pollution from the waste
tires, which is becoming a troublesome issue all around
the world. It is reported that 240 million waste tires in the
United States, 40 million in the UK, and 10 million in Aus-
tralia are generated annually.[1] A number of approaches
have been suggested to recycle the waste tires, such as
pavements, pyrolysis to recover different chemicals.[2]
However, some of the approaches have been proven uneco-
nomical and inefficient with respect to processing the large
quantity of waste tire generated every year. Among the
approaches for recycling the waste tire, one economical and
promising approach is to shred and ground the waste tire to
scrap rubber powder (SRP) and then to compound SRP with
thermoplastics to form thermoplastic elastomer (TPE).[3,4]
Using this approach, large quantity of waste tire can be

Macromol. Mater. Eng. 2004, 289, 360–367 DOI: 10.1002/mame.200300311 ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Thermoplastic Elastomers Derived from Scrap Rubber Powder/LLDPE Blend with LLDPE-graft-(Epoxidized Natural Rubber) . . . 361

reused, as SRP is the major component in preparation of
TPE.
SRP has been used as base materials for TPE for some
time. J Karger-Kocsis et al. prepared LDPE-based thermo-
plastic elastomers containing ground tire rubber.[5] Only
25 wt.-% SRP was used and the composition was LDPE:
rubber:GTR ¼ 50:25:25 wt.-%. Also 25 wt.-% fresh gum
(SBR, NR and EPDM rubbers) was used as elastomeric
materials. The composites reported are actually not stan-
dard TPE in view of the low elongation at break (12–61%).
S. K. De et al. used SRP to replace one half of EPDM in the
dynamically vulcanized EPDM/acrylic-modified HDPE
blends.[6] Higher elongation at break was reported. Still
low content SRP was used and some of the samples had bad
re-processibility. TPE based on maleic anhydride-SRP has
also been reported.[7] Generally, a suitable compatibilizer is
needed to add into the SRP/thermoplastics blends to en-
hance the interfacial properties. Many researchers have
tried peroxide such as dicumyl peroxide (DCP) to improve
the interfacial properties. But DCP may also cause cross-
linking of some thermoplastics such as polyethylene.
Therefore it is not strange that some compositions with
DCP had low or no reprocessibility.[5–7]
In the present paper, we attempt to prepare TPE from SRP
and linear low-density polyethylene (LLDPE). Higher
content of SRP (up to 70 wt.-%) was used. A novel dual
compatibilizer system comprising of epoxidized natural
rubber and LLDPE graft was utilized to compatibilize the
SRP/LLDPE system. The effects of the composition of the
dual compatibilizer on the mechanical properties and
processibility were studied. The morphology and structure
of the blend were investigated using SEM, TEM and DSC.
Experimental Part
Raw Materials
Cryogenically made SRP with different mesh size by sieving
was purchased from Guangdong Faxing Rubber Plastics Co.
Ltd. (China). Analysis of SRP by thermogravimetry yiel-
ded 59.5 wt.-% rubber hydrocarbon content, 6.8 wt.-% oil,
30.4 wt.-% carbon black and 3.5 wt.-% ash. The composition of
the rubber hydrocarbon is 37.2% natural rubber, 19.2%
polybutadiene and 3.1% styrene-butadiene rubber. The SRP
sample was dried at 80 8C for 24 h before compounding.
Commercial LLDPE [melt flow index (MFI) ¼ 6.9 g/10 min;
Guangzhou Petroleum Chemical Plant, China] was used as
received.
LLDPE solid-phase graft (LLDPE-g-VM) was prepared
according to ref.[8] with maleic anhydride, methyl methacry-
late and butyl acrylate as the grafting monomers. The grafting
percentage (GP) was calculated according to the below
equation:
WgP
WPE
GPð%Þ ¼  100 ð1Þ
WPE
where WgP is the sample mass after extraction and WPE is the
mass of LLDPE in the sample. The grafting percentage of
LLDPE-g-VM was determined as 13.1%. The epoxidized
natural rubber with epoxidization content of 50% was obtained
from South China Institute of Tropical Plants.
Preparation of SRP/LLDPE Blends
The formulations of the SRP/LLDPE blends are summarized in
Table 1. In all the formulations, the rubber/plastics ratio is kept
constant at 70/30, viz. amount of SRP and ENR is 70 phr while
that of LLDPE and LLDPE-g-VM is 30 phr. The weight ratio
between ENR and LLDPE-g-VM is defined as k. The particle
size of the SRP is 420 mm unless stated otherwise. The ingre-
dients of the SRP/LLDPE blends were compounded with open
two-roller mill at 120 8C for 6 min and compressively moulded
at 170 8C for 5 min and room temperature for 10 min.
Mechanical Properties
Tensile and tear testing were cut from 1 mm thick sheet and
tested using a Shimadzu AG-1 electron tensile tester according
to ISO/DIS37-1990 and ISO034-1979 respectively. Shore A
hardness was measured according to ISO7619-1986.
Melt Flow Index
Melt flow measurements were carried out using an XNR-400III
MFI tester, China at temperature of 230 8C and loading of
5.0 kg.
Morphology Observation
Tensile fractured surfaces were gold coated and observed using
a LEO1530 VP scanning electronic microscopy. TEM obser-
vations were performed with JEM-100CX TEM.
Differential Scanning Calorimetry
The TA Modulated DSC 2910 was employed to test the thermal
transitions of the blends. Circa 15 mg sample was first cooled
down to
150 8C and then heated to 200 8C at a heating rate of

Table 1. Formulations of compatibilized SRP/LLDPE blends with different k values.

k – 0 0.5 1 1.5 2 2.5 3

SRP/wt.-% 70 70 67.5 65 62.5 60 57.5 55
ENR/wt.-% – – 2.5 5 7.5 10 12.5 15
LLDPE-g-VM/wt.-% – 5 5 5 5 5 5 5
LLDPE/wt.-% 30 25 25 25 25 25 25 25

Macromol. Mater. Eng. 2004, 289, 360–367 www.mme-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
362
Figure 1. FTIR spectra of neat LLDPE and LLDPE-g-VM.
20 8C/min. Nitrogen with a flow rate of 40 ml/min was used as
purge gas.
Results and Discussion
Interaction Mechanism in the Compatibilized Systems
Most of MAH grafted onto LLDPE is changed to maleic
acid as the product has experienced several times of wash-
ing with water. Therefore, the possible monomers onto the
LLDPE backbone are maleic acid, MMA, BA and small
amounts of MAH. The spectra obtained from FTIR
measurements of the LLDPE before and after functionaliza-
tion by MAH, MMA and BA is shown in Figure 1. The spectra
of the corresponding monomers of the graft, i.e. maleic acid,
MMA and BA are given in Figure 2. These three monomers
Scheme 1. Interaction mechanism in the compatibilized systems.
Macromol. Mater. Eng. 2004, 289, 360–367 www.mme-journal.de
B. Guo, Y. Cao, D. Jia, Q. Qiu
Figure 2. Spectra of the corresponding monomers of LLDPE-g-
VM.
show the carbonyl absorption at 1 704 cm
1, 1 728 cm
1 and
1 728 cm
1 respectively. The broad absorption band around
1 716 cm
1 in the spectrum of the LLDPE-g-VM is char-
acteristic of the carbonyl groups in maleic acid, MMA and
BA. Therefore, it is confirmed that both maleic acid, MMA
and BA are grafted onto the LLDPE backbone.
Maleic acid and MAH containing LLDPE-g-VM may
react with epoxidized natural rubber in the presence of
tertiary amine, such as 2,4,6-tris(dimethylaminomethyl)-
phenol (DMP-30). The mechanism is as follows.
On one hand, maleic acid reacts with the epoxy rings on
the ENR backbone to form ester linkage between the two
components. On the other hand, tertiary amine attacks anhy-
dride groups on the graft to form carboxylate anions. The
carboxylate anion then reacts with the ENR to open the
epoxy ring. This process is illustrated in Scheme 1.
ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Thermoplastic Elastomers Derived from Scrap Rubber Powder/LLDPE Blend with LLDPE-graft-(Epoxidized Natural Rubber) . . . 363

Table 2. Effect of k value on MFI of SRP/LLDPE blends.
k 0.5 1 1.5 2 2.5
MFI/(g/10 min) 1.8 1.6 1.4 1.2 0.9
Conventionally, the MAH polyolefin grafts by melt
grafting have relatively low grafting percentage. The MAH
grafting efficiency could be improved by solid grafting
technique and using co-monomers.[8] In the present work,
LLDPE-g-VM was prepared by solid grafting technique
with MAH, MMA and BA. The graft was used as compa-
tibilizer for the SRP/LLDPE systems. Actually, MMA and
BA were used mainly to improve the content of MAH in the
PE graft. Since MAH (maleic acid) is the main site for
reaction with the epoxide, the substantially enhanced MAH
(maleic acid) content in the graft will effectively improve
the interactions between the PE graft and ENR. Due to the
low MAH content, the pair of LLDPE-g-MAH/ENR has
been proven to be ineffective in this system.
Thermodynamically, LLDPE-g-VM has good compat-
ibility with LLDPE while the ENR may penetrate into SRP
network and crosslink with the residue double bonds
present on the SRP surfaces. In the mean time, as illustrated
above, the graft may chemically bond with ENR. Therefore
the ENR/LLDPE-g-VM dual compatibilizer has the poten-
tial to greatly improve the compatibility between SRP and
LLDPE.
blends have k value of 1.5. As shown, the blend with 840 mm
SRP had worst properties and the blends with finer SRP have
3
similar properties. The blends have continuous-discontin-
0.8 uous morphology and LLDPE constitutes the continuous
phase (this will be substantiated with SEM results). Gene-
rally, the blend with continuous-discontinuous morphology
has optimal properties when the size of the discontinuous
phase is in micrometer scale. The finest SRP in the present
study (177 mm) is still far above this scale. Therefore, the
interfacial properties of the blends are more important in
determining the mechanical properties than the SRP
particle size.
Effects of Compatibilizer Ratio on the Mechanical
Properties of SRP/LLDPE Blends
The effects of the compatibilizer ratio k on the mechanical
properties are shown in Figure 3 to Figure 5. For the control
sample (no compatibilizer), the tensile strength, tear stren-
gth, elongation at break and permanent set is 5.8 MPa,
39.4 kN  m
1, 160% and 36% respectively. As shown in
Figure 1 and Figure 2, the mechanical properties of the
blend compatibilized by LLDPE-g-VM only (k ¼ 0) are
almost the same or worse compared with the control sam-
ple. In addition, the tensile strength, tear strength, elonga-
tion at break and permanent set of the blend compatibilized

Effects of Compatibilizer Ratio on the Melt Flow

Index of SRP/LLDPE Blends
MFI, which reflects the flowability of thermoplastics in the
melting state, is one of the important factors controlling the
processibility of the polymer. The MFI of the blends with
different compatibilizer ratio is summarized in Table 2. As
indicated by the MFI data, all the compatibilized blends
have good processibility. The MFI decreased with k. This
may be due to the enhanced molecular weight of the blend
with higher ENR content.

Effects of SRP Particle Size on Mechanical

Properties of Compatibilized Blends
The effects of the SRP size on the mechanical properties of Figure 3. Effects of k value on tensile strength and tear strength
the compatibilized blends are shown in Table 3. All the of SRP/LLDPE blends.

Table 3. Effects of particle size of SRP on tensile strength and tear strength of SRP/LLDPE blends.

Average particle size Tensile strength Tear strength Elongation at break Permanent set Shore A hardness

1
mm MPa kN  m % %
840 6.7 38.7 140 12 80
420 9 49.6 295 28 84
250 8.5 45.7 280 28 82
177 8.8 46 265 28 83

Macromol. Mater. Eng. 2004, 289, 360–367 www.mme-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
364 B. Guo, Y. Cao, D. Jia, Q. Qiu

Figure 4. Effects of k value on elongation at break and

permanent set of SRP/LLDPE blends.
Figure 5. Effects of k value on hardness of SRP/LLDPE blends.

Figure 6. Surface of SRP particles of various composites (a) without compatibilizer (b) ENR (c)
LLDPE-g-VM (d) LLDPE-g-VM/ENR.

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 Thermoplastic Elastomers Derived from Scrap Rubber Powder/LLDPE Blend with LLDPE-graft-(Epoxidized Natural Rubber) . . . 365

Figure 7. Fracture surface of SRP/LLDPE blend before (a) and after (b) compatibilized with
ENR/LLDPE-g-VM (c) and (d) Surface of the SRP/LLDPE specimen before (c) and after (d)
compatibilized with ENR/LLDPE-g-VM.

Figure 8. TEM photos (magnification of 4 400) of SRP/LLDPE blends before (a) and after (b)
compatibilized with ENR/LLDPE-g-VM.

Macromol. Mater. Eng. 2004, 289, 360–367 www.mme-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
366
Figure 9. Comparisons of DSC traces of SRP/LLDPE blend
before and after compatibilization.
by ENR only (the weight ratio of SRP/ENR/LLDPE is 65/5/
30) is 4.6 MPa, 31.9 kN  m
1, 100% and 40%. Therefore
the blend compatibilized by each compatibilizer itself has
worse performance compared with the control sample. The
mechanical properties were almost independent of the dual
compatibilizer content when k was higher than 1.5, sug-
gesting that the interface was saturated when k was 1.5 and
the excess compatibilizer may separate from the interphase
between SRP and LLDPE. The blend had better perfor-
mance at the ratio of 1.5. In addition, as indicated in Figure 5,
the hardness of the blend decreased slightly with k, which
may probably be due to the decreased vulcanizate (SRP)
content in the blend with higher ENR content. According to
the definition of thermoplastic elastomer in ASTM, the
elongation at break and permanent set of the thermoplastic
elastomer should be above 200% and below 50% respec-
tively. Therefore the SRP/LLDPE blends compatibilized by
the dual compatibilizer ENR/LLDPE are actually standard
thermoplastic elastomer with good mechanical properties.
Morphology Observations
Figure 6 shows the fracture surface of the blends before and
after compatibilization (k ¼ 1.5). As shown, ENR could
penetrate into SRP while the LLDPE stays on the surface of
the SRP and acts as emulsifier between SRP and LLDPE.
The SRP has better adhesion with ENR than with LLDPE-
g-VM. The morphology shown in Figure 6(d) is apparently
different from Figure 6(b) and Figure 6(c). The matter on
the SRP surface, unlike ENR or LLDPE-g-VM, may be the
reacted dual compatibilizer. Figure 7(a) and Figure 7(b), in
lower magnification, show the fracture surface of the blend
before and after compatibilized with the dual compatibili-
zer. It is very clear that the compatibilized blend has less
cavity and enhanced interfacial adhesion.
Figure 7(c) and Figure 7(d) compare the specimen sur-
face of the blend before and after being compatibilized with
the dual compatibilizer. As shown, the compatibilized blend
Macromol. Mater. Eng. 2004, 289, 360–367 www.mme-journal.de
B. Guo, Y. Cao, D. Jia, Q. Qiu
has apparently smooth surface, also suggesting better dis-
persion of the SRP and higher interfacial adhesion.
To study the effects of the dual compatibilizer on the
interfacial adhesion further, the TEM observations were
performed on the blend before and after being compatibi-
lized with the dual compatibilizer. As shown in Figure 8(a),
the simple blend has very sharp interface, suggesting the
very low adhesion between SRP (dark phase) and LLDPE
(bright phase). The compatibilized blend, as shown in
Figure 8(b), has improved interfacial adhesion. Apparent
penetrations and diffusion between the two phases were
observed. A light colored interphase formed between SRP
and LLDPE. This formation may be due to the reactions
between ENR and LLDPE-g-VM as illustrated in Scheme
1. In addition, some ENR particles with several micrometer
were found to be entrapped in LLDPE matrix. This would
be beneficial to the deformation of the blends under stress.
Differential Scanning Calorimetry
In view of the substantial increase in mechanical properties
after compatibilization, the thermal transitions may also be
different after modification with the dual compatibilizer.
The DSC traces of the blend before and after compatibiliza-
tion are shown in Figure 9. DSC results showed a distinct
glass transition at 74 8C, suggesting the formation of inter-
facial region. As a consequence, the improvement in mech-
anical properties was attributed to the formation of the
interfacial region of the blend.
Conclusions
The ENR/LLDPE-g-VM dual compatibilizer modified
SRP/LLDPE is a standard thermoplastic elastomer with
good elasticity and comprehensive mechanical properties.
It has potential applications in recycling SRP in large
quantities and as environmentally friendly materials.
SEM and TEM results showed that the blend compati-
bilized with the dual compatibilizer had apparently impro-
ved interfacial adhesion. The morphology was a typical
continuous-discontinuous structure. LLDPE constituted
continuous phase and SRP constitutes discontinuous phase.
DSC results showed a distinct glass transition at 74 8C,
suggesting the formation of interfacial region. The improve-
ment in mechanical properties was attribute to the enhanced
interfacial properties of the blend.
Acknowledgement: Supported by the Natural Science
Foundation of China (Grant Numbers 59933060 and 50003004).
[1] S. N. Bhattacharya, I. Sbarsk, Plast. Rubber Compos. Proc.
Appl. 1998, 27, 317.
ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Thermoplastic Elastomers Derived from Scrap Rubber Powder/LLDPE Blend with LLDPE-graft-(Epoxidized Natural Rubber) . . . 367

[2] T. Amari, N. J. Themelis, I. K. Wernick, Resources Policy [6] A. K. Naskar, A. K. Bhowmick, S. K. De, Polym. Eng. Sci.
1999, 25, 179. 2001, 41, 1087.
[3] K. Oliphant, W. E. Baker, Polym. Eng. Sci. 1993, 33, 166. [7] A. K. Naskar, S. K. De, A. K. Bhowmick, J. Appl. Polym. Sci.
[4] J. Michel, W. E. Baker, Plast. Rubber Compos. Proc. Appl. 2002, 84, 370.
1991, 15, 87. [8] D. M. Jia, Y. F. Luo, Y. M. Li et al., J. Appl. Polym. Sci. 2000,
[5] C. R. Kumar, I. Fuhrmann, J. Karger-Kocsis, Polym. Degrad. 78, 2482.
Stab. 2002, 76, 137.

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