Effect of the Compatibiliser on the Morphology and Properties of Dynamically Cured PP/EPDM/Epoxy Blends

Effect of the Compatibiliser on the Morphology and Properties of

Dynamically Cured PP/EPDM/Epoxy Blends
Xueliang Jiang*
State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, 200030
Received: 11 June 2006 Accepted: 3 August 2006

SUMMARY
Dynamic vulcanisation was successfully applied to epoxy resin reinforced polypropylene (PP)/ethylene-
propylene diene elastomer (EPDM) blends, and the effects of different compatibilisers on the morphology
and properties of dynamically cured PP/EPDM/epoxy blends were studied. The results show that dynamically
cured PP/EPDM/epoxy blends compatibilised with maleic anhydride-grafted polypropylene (MAH-g-PP) have
a three-phase structure consisting of EPDM and epoxy particles dispersed in the PP continuous phase, and
these blends had improved tensile strength and flexural modulus. While using maleic anhydride-grafted EPDM
(MAH-g-EPDM) as a compatibiliser, the structure of the core-shell complex phase and the PP continuous phase
showed that epoxy particles could be embedded in MAH-g-EPDM in the blends, and gave rise to an increase in
impact strength, while retaining a certain strength and modulus. DSC analysis showed that the epoxy particles
in the blends compatibilised with MAH-g-PP were more efficient nucleating agents for PP than they were in the
blends compatibilised with MAH-g-EPDM.

1. INTRODUCTION maintaining the stiffness-to-toughness polypropylene (MAH-g-PP) was used

PP has an important place among
the synthetic polymers because of its
growing commercial applications.
However, its application as a structural
material is somewhat limited because
of its relatively low impact resistance.
The impact toughness of PP can be
improved dramatically by the addition
of elastomers, such as ethylene
propylene rubber (EPR), ethylene-
propylene diene elastomer (EPDM),
ethylene-octene copolymer (POE)
and styrene-ethylene butylene-styrene
triblock copolymer (SEBS) 1-2.
balance5-6.
Dynamic vulcanisation is an effective
method of preparing thermoplastic
vulcanisate materials7-9. It consists of
vulcanising an elastomer during its
melt-mixing with a molten plastic.
This technology has led to a significant
number of new thermoplastic elastomer
products, commercialised during the
mid- to late-1980s10. However, there
are few papers concerning the dynamic
vulcanisation of thermoplastic resin/
thermosetting resin blends.
as a compatibiliser. Dynamic cure of
the epoxy resin led to an improvement
in the modulus and stiffness of the
PP/epoxy blends, and the addition
of MAH-g-PP resulted in increased
impact strength and tensile strength.
In this work, the morphology, toughness
and stiffness of blends made by the
dynamic cure of an epoxy resin in
PP/EPDM, were investigated, using
maleic anhydride-grafted EPDM
(MAH-g-EPDM) and MAH-g-PP as
compatibilisers.

The incorporation of elastomers into
PP leads to a drastic reduction in the
modulus and strength. Therefore,
issues concerning the simultaneous
reinforcing and toughening of PP have
attracted considerable attention3-4. The
incorporation of inorganic fillers or
short glass fibres into PP/elastomer
blends provides an attractive means of
*Corresponding author. XL Jiang, E-mail: jxl110@sjtu.edu.cn
©
Rapra Technology, 2007
Our laboratory has used dynamic
vulcanisation to prepare a new
type of polypropylene (PP)/epoxy
blend11-12. The blends were prepared
in the mixing chamber of a Haake
rheometer RC90 by dynamically
curing an epoxy resin in the molten PP.
Because the epoxy resin and PP were
immiscible, maleic anhydride-grafted
2. EXPERIMENTAL
2.1 Materials
PP, grade F401, was produced by
Yangzi Petrochemical Co. Ltd. (China),
with a melt flow index (MFI) of 1.9 dg/
min (230 °C, 2.16 kg). Diglycidyl
ether of bisphenol-A resin (DGEBA,
Mw: 4500 g/mol) was supplied by
Shanghai Resin Co. Ltd. (China). The
curing agent, 2-ethylene-4-methane-
imidazole (EMI-2,4) was produced by
Shanghai Chemical Agent Company
(China). MAH-g-PP and MAH-g-

Polymers & Polymer Composites, Vol. 15, No. 2, 2007 145

 Xueliang Jiang

EPDM with MAH content of 1% 2.5 DSC Analysis the chemical reactivity and extent of
were prepared by Shanghai Sunny reaction in reactively compatibilised
The crystallisation behaviour of PP
New Technology Development Co. blends.
and the curing behaviour of the epoxy
Ltd. (China).
resin in the blends were analysed using
a Perkin-Elmer DSC (Paris 1) (USA) Figure 1 shows the relationship between
2.2 Sample Preparation in a nitrogen atmosphere. the torque and time for PP/EPDM/epoxy
blends at 190 °C. The addition of 10 wt%
Before blending, MAH-g-PP, MAH-
Samples of about 4 mg were taken from MAH-g-PP or MAH-g-EPDM to the
g-EPDM and epoxy resin were dried
the moulded plaques. Nonisothermal PP/EPDM/epoxy blends obviously
at 80 °C under vacuum for about
crystallisation was performed as increased the torque at equilibrium.
8 h. Unless otherwise specified,
follows: a sample was first heated As MAH-g-PP and MAH-g-EPDM
dynamically cured blends were
to 200 °C at 50 °C/min and then both contain active maleic anhydride
prepared in the mixing chamber of a
maintained at this temperature for (MAH) groups, the functional groups
Haake Rheometer RC90 at 190 °C and
5 min in order to eliminate any previous can react with the hydroxyl or epoxy
50 rpm. MAH-g-PP or MAH-g-EPDM
thermal history. The sample was groups of the epoxy resin in the blends,
and PP were first mixed for 2 min,
subsequently cooled down to 40 °C and the reactions lead to an increase in
then the epoxy resin was added. Two
at a cooling rate of 10°C/min and then the viscosities of the blends through
min later, the curing agent was added
heated to 200 °C at 10 °C/min for data the addition of MAH-g-PP or MAH-g-
with the mixing continuing. The total
collection. The curing of the epoxy EPDM. Shieh13 reported using MAH-
mixing process lasted about 10 min.
resin in the blends was performed as g-PP and a multifunctional epoxy resin
The composition was removed from
follows: the sample was heated from as dual reactive compatibilisers for
the mixer and compression-moulded in
40 °C to 200 °C at 10 °C/min. PP/poly(butylene terephthalate) (PBT)
a press at 195 °C for 10 min, then cold
blends.
pressed to give samples for testing.
3 RESULTS AND As shown in Figure 1, the addition of
2.3 Measurements of DISCUSSION the curing agent (EMI-2,4) at the mixing
Mechanical Properties time of 4 min led to an obvious rise in
3.1 Compatibilisation and
The tensile properties were measured the torque of the PP/EPDM/epoxy
Dynamic Cure blends. This shows that the epoxy resin
using an Instron 4465 Tester (USA)
at a crosshead speed of 20 mm/min Torque measurements can be used had been cured by EMI-2,4 during its
according to ASTM D638. Notched to give qualitative information about mixing with molten PP and EPDM. The
Izod impact strengths were tested
using a Ray-Ran Universal Pendulum
Figure 1. Plot of torque versus time for PP/EPDM/EP blends at 190 °C; (a) PP/
Impact Tester (UK) at an impacting
EPDM/EP=75/25/10; (b) PP/MAH-g-PP/EPDM/EP=65/10/25/10; (c) PP/EPDM/
pendulum speed of 3.5 m/s, according
MAH-g-EPDM/EP=75/15/10/10; (d) PP/EPDM/EP/EMI-2,4=75/25/10/0.4; (e) PP/
to ASTM D256. Flexural properties EPDM /MAH-g-EPDM/EP/EMI-2,4=75/15/10/10/0.4; (f) PP/MAH-g-PP/EPDM/
were measured using the Instron 4465 EP/EMI-2,4=65/10/25/10/0.4
Tester and a three-point-loading rig, at
a speed of 1.7 mm/min., according to
ASTM D790. In each of the tests, at
least five samples were tested, and the
average results were reported.

2.4 Scanning Electron

Microscopy (SEM)
A scanning electron microscope
(SEM, HITACHI-S-2150) was used
to examine the morphology of the
samples. All the samples were fractured
in liquid nitrogen. The samples were
etched using n-heptane for 10 min, and
then covered with a thin gold layer for
further observation.

146 Polymers & Polymer Composites, Vol. 15, No. 2, 2007

 Effect of the Compatibiliser on the Morphology and Properties of Dynamically Cured PP/EPDM/Epoxy Blends

curing behaviour of the epoxy resin Figure 2. DSC curves of (a) EP/EMI-2,4 (100/4); (b) PP/MAH-g-PP/EP/EMI-
in the blends can be analysed from 2,4=60/10/30/1.2 and (c) PP/EP/EMI-2,4=70/30/1.2
the DSC curves. Figure 2 shows the
DSC heating scans of epoxy/EMI-2,4
and dynamically cured PP/EPDM/
epoxy (75/25/10) blends. There was
an obvious exothermal enthalpy
reaction resulting from the curing
of the epoxy/EMI-2,4 blend, and the
curing temperatures ranged from 80
to 150 °C. No exothermic enthalpy
associated with the curing reaction
could be seen in the dynamically cured
PP/EPDM/epoxy (75/25/10) blend,
only the enthalpy of fusion of the PP.
This shows that the epoxy resin was
fully cured.
Figure 3. SEM photographs of the etched blends
3.2 SEM Analysis
Figure 3 shows the effect of the
different compatibilisers on the
morphology of dynamically cured PP/
EPDM/epoxy blends. To distinguish
the phase structure of each component
in the blends, the EPDM in the samples
was etched using n-heptane. For the
PP/EPDM (75/25) blend (Figure 3a),
the holes with diameters of 3–8 μm
show that the EPDM was dispersed (a) (b)
in the PP matrix. In the case of the
PP/EPDM/MAH-g-EPDM (75/15/10)
(Figure 3b) and PP/MAH-g-PP/
EPDM (65/10/25) (Figure 3c) blends,
their morphology was similar to that
of PP/EPDM (75/25).

Figure 3d shows the etched SEM

micrograph of the dynamically cured
PP/EPDM/epoxy (75/25/10) blend.
Holes representing EPDM and epoxy
particles with similar diameters of (c) (d)
about 3–8 μm existed in the PP matrix.
This shows that there was a three-phase
structure in the dynamically cured
PP/EPDM/epoxy blends, probably
an EPDM dispersed phase, a epoxy
dispersed phase and a PP continuous
phase. A few smaller epoxy particles
with diameters of about 0.2–0.4 um and
a number of smaller holes representing
etched EPDM were observed in the
dynamic cured PP/EPDM/MAH-g-
EPDM/epoxy (75/15/10/10) blend. The (e) (f)
number of EPDM holes was greater

Polymers & Polymer Composites, Vol. 15, No. 2, 2007 147


in this blend than in the analogous
PP/EPDM/epoxy (75/25/10) blend. It
can be concluded that MAH-g-EPDM
improves the compatibility between the
PP and epoxy resin.
The epoxy particles could be embedded
in MAH-g-EPDM, and form the
structure of core-shell complex phase
and PP continuous phase in the blend.
Similar structures of three-component
polymer/elastomer/fillers have been
reported by other authors14-15. When
MAH-g-EPDM and EPDM were
etched by n-heptane, a lot of epoxy
particles were detached along with
the MAH-g-EPDM and EPDM. The
dynamically cured PP/MAH-g-PP/
EPDM/epoxy (65/10/25/10) blend
(Figure 3f) has a structure with the
holes from EPDM and there were
a number of epoxy particles with
diameters of about 0.2-0.5 um in
the PP matrix. The number of holes
left by the epoxy particles was more
than had been seen in the case of the
dynamically cured PP/EPDM/MAH-
g-EPDM/epoxy (75/15/10/10) blend.
This shows that MAH-g-PP can
improve the compatibility between
PP and epoxy resin. There was also a
three-phase structure of PP/MAH-g-
PP/EPDM/epoxy blends, consisting of
an EPDM dispersed phase, an epoxy
dispersed phase and a PP continuous
phase.
3.3 Mechanical Properties
Most chemically different polymers are
immiscible, and blending them leads to
materials with weak interfacial adhesion
and poor mechanical performance.
The conversion of the immiscible
blend to a useful polymeric product
with the desired properties requires
manipulation of the interface. One of
the classical routes to ensure adhesion
between phases is the use of a third
component, known as a compatibiliser,
which is compatible or miscible with
both phases14. As in this case the epoxy
resin is immiscible with EPDM and PP,
MAH-g-EPDM and MAH-g-PP were
used as compatibilisers.
148
Xueliang Jiang
Figure 4 shows the effect of different
compatibilisers on the mechanical
properties of the dynamically cured PP/
EPDM/epoxy blends. With the same
proportion of epoxy resin, the tensile
strength and flexural modulus of the
dynamically cured PP/EPDM/epoxy
blends compatibilised with MAH-g-
PP were higher than those of the non-
compatibilised blends and the blends
compatibilised with MAH-g-EPDM,
but the impact strength was obviously
lower; the non-compatibilised blends
had the lowest impact strength. With
increasing epoxy resin content, the
tensile strength and flexural modulus
of all the dynamically cured PP/EPDM/
epoxy blends increased gradually,
but the elongation at break decreased
dramatically. In the case of the
dynamically cured PP/EPDM/epoxy
blends compatibilised with MAH-g-
EPDM, the impact strength increased
with increasing epoxy resin content
(0–10 wt%) and reached a maximum
of 370 J/m at an epoxy resin content
of 10 wt%.
When the epoxy resin content was over
10 wt%, the impact strength decreased.
But for the dynamically cured PP/
EPDM/epoxy blends compatibilised
with MAH-g-PP and also in the case
of non-compatibilised blends, the
impact strength decreased slightly with
increasing epoxy resin content. The
results show that the dynamically cured
PP/EPDM/epoxy blends compatibilised
with MAH-g-EPDM or MAH-g-PP
had better mechanical properties than
the non-compatibilised analogues, but
the effect of different compatibilisers
on the mechanical properties was
different. Blends compatibilised with
MAH-g-PP had higher tensile strength
and flexural modulus values, but blends
compatibilised with MAH-g-EPDM
had higher impact strength.
The different mechanical properties of
the dynamically cured PP/EPDM/epoxy
blends compatibilised with MAH-g-
EPDM or MAH-g-PP can be attributed
to their distinct morphology. When
MAH-g-PP was used as compatibiliser,
Polymers & Polymer Composites, Vol. 15, No. 2, 2007
dynamically cured PP/EPDM/epoxy
blends had epoxy resin particles finely
dispersed in the PP matrix, and the
cured epoxy particles acted as organic
fillers to increase the stiffness of the
blends. When MAH-g-EPDM was
used as compatibiliser, the blends had
epoxy particles containing embedded
MAH-g-EPDM and EPDM which
obviously improves its toughness,
whereas a higher epoxy resin content
(10 wt%) can be expected to impair
the toughness. Faulkner16-17 studied
the impact behaviour of PP/mica/
elastomer composites and tried to
optimise stiffness and toughness, and
thought that the embedded structure
had better impact resistance.
3.4 DSC Analysis
PP can crystallise rapidly, even under
quenching conditions. Figure 5 shows
the first cooling and second heating
DSC scans of PP, PP/EPDM (75/25),
PP/epoxy (75/25), dynamically cured
PP/EPDM/epoxy (75/25/10), dynamic
cured PP/EPDM/MAH-g-EPDM/
epoxy (75/15/10/10) and dynamically
cured PP/MAH-g-PP/EPDM/epoxy
(65/10/25/10). Table 1 gives a summary
of the crystallisation and melting data
from the DSC thermograms. The
crystallinity of the PP component in
the blends was calculated by using the
following equation:
Xc (%) = (H/H0) ×(100/x) (1)
where Xc is the crystallinity of PP, H
is the measured heat of crystallisation
of the blend, H0 (=170 J/g) is the heat
of crystallisation of 100% crystalline
isotactic polypropylene18, and x is the
mass fraction of polypropylene in the
blend.
Only a single crystallisation peak
(Tp) could be seen for PP, PP/EPDM,
PP/epoxy and all the dynamically
cured PP/EPDM/epoxy blends. All
the crystallisation peak temperatures
of the blends were higher than the
crystallisation peak of PP (113.1 °C).
A shift of the crystallisation peak to a
 Effect of the Compatibiliser on the Morphology and Properties of Dynamically Cured PP/EPDM/Epoxy Blends

Figure 4. Effect of different compatibilisers on the mechanical properties of dynamically cured PP/EPDM/EP blends.
Formulation: (PP +MAH-g-PP 10)75, (EPDM+MAH-g-EPDM 10) 25, EP variable, EMI-2,4 (4 parts per 100 parts EP)

(a) (b)

(c) (d)

Figure 5. DSC thermograms at first cooling and second heating of (a) PP; (b) PP/EPDM=75/25; (c) PP/epoxy=75/25; (d)
PP/EPDM/epoxy/EMI-2,4=75/25/10/0.4; (e) PP/EPDM/MAH-g-EPDM/epoxy/EMI-2,4=75/15/10/10/0.4; (f) PP/MAH-g-PP/
EPDM/epoxy/EMI-2,4 = 65/10/25/10/0.4

(a) (b)

Polymers & Polymer Composites, Vol. 15, No. 2, 2007 149


Table 1. DSC analysis results of PP and PP/epoxy blends (Tm: peak melting
temperature; Tc: peak crystallisation temperature; Xc: the crystallinity of PP)
Composition
PP
PP/EPDM=75/25
PP/epoxy = 75/25
PP/EPDM/epoxy/EMI-2,4 = 75/25/10/0.4
PP/EPDM/MAH-g-EPDM/epoxy/EMI-2,4=75/15/10/10/0.4
PP/MAH-g-PP/EPDM/epoxy/EMI-2,4 = 65/10/25/10/0.4
higher temperature suggests that EPDM,
MAH-g-EPDM and epoxy resin in the
blends can act as nucleating agents,
accelerating the crystallisation of PP.
The Tp of PP in PP/EPDM (75/25) was
about 118.2 °C, i.e. lower than that of
the PP/epoxy (75/25). The result shows
that the epoxy resin was a more efficient
nucleating agent than EPDM.
The Tp of PP in the dynamically
cured PP/MAH-g-PP/EPDM/epoxy
(65/10/25/10) was higher than that of PP
in the PP/epoxy (75/25), dynamically
cured PP/EPDM/epoxy (75/25/10) and
dynamic cured PP/EPDM/MAH-g-
EPDM/epoxy (75/15/10/10), showing
that the smaller epoxy resin particles
in the dynamically cured MAH-g-PP/
EPDM/epoxy blends had resulted in an
increase of the number of nucleating
sites, increasing the crystallisation
peak temperature of PP. The Tp of
dynamically cured PP/EPDM/MAH-g-
EPDM/epoxy (75/15/10/10) was about
119.7 °C, which is similar to that of
PP/EPDM (75/25), but lower than that
of the dynamically cured PP/EPDM/
epoxy (75/25/10). Although there were
many smaller epoxy particles in the
blends, the epoxy particles could have
contained embedded MAH-g-EPDM
and EPDM, decreasing the nucleating
effect of the epoxy resin. Premphet
et al.15 also found that the nucleating
effect of calcium carbonate on PP in
PP/CaCO3/elastomers became worse
when the CaCO3 was embedded in the
elastomer. In all cases, the crystallinity
of PP in the blends was higher than that
150
Xueliang Jiang
Tm, °C Tc, °C Xc,
wt%
162.3 113.1 56.1
164.3 118.2 57.5
165.2 124.2 56.7
165.4 125.8 57.9
163.9 119.7 59.1
164.2 129.6 60.8
of pure PP (162.3 °C), and the increase
in the melting temperature of PP in the
blends was directly related to the size
of the PP crystals19.
4. CONCLUSIONS
The effects of different compatibilisers
on the morphology and properties of
dynamically cured PP/EPDM/epoxy
blends have been studied. Blends
compatibilised by MAH-g-PP with a
three-phase structure of EPDM and
epoxy particles dispersed in the PP
continuous phase were obtained, and
they showed improved tensile strength
and flexural modulus, although
the impact strength varies slightly.
When MAH-g-EPDM was used as
compatibiliser, the blends possessed
a structure consisting of a core-shell
complex phase and a PP continuous
phase, with epoxy particles embedded
in MAH-g-EPDM and EPDM in
the blends. The core-shell structure
gave rise to an increase in the impact
strength, maintaining certain strength
and modulus. DSC analysis showed that
the epoxy particles in the dynamically
cured PP/MAH-g-PP/EPDM/epoxy
blends were more efficient nucleating
agents than those in the equivalent PP/
EPDM/MAH-g-EPDM/epoxy blends,
but the nucleating effect of epoxy
particles embedded in the elastomer on
PP in the blends became worse.
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