Polymer 41 (2000) 6765–6771

Polypropylene-block-poly(ethylene-co-propylene) addition to
polypropylene/poly(ethylene-co-propylene) blends: morphology and
mechanical properties
K. Nitta a,*, T. Kawada a, M. Yamahiro b, H. Mori b, M. Terano b
a
Center for New Materials, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Tatsunokuchi, Ishikawa 923-1292, Japan
b
School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Tatsunokuchi, Ishikawa 923-1292, Japan
Received 19 November 1998; received in revised form 14 June 1999; accepted 24 November 1999

Abstract
The additive effects of a diblock copolymer of polypropylene and ethylene–propylene rubber PP-b-EPR(50–50) on the morphology and
mechanical properties of PP/EPR(50/50) blends were investigated. It was found from an electron microscopy study that the block copolymer
is compatible with the PP phase but incompatible with the EPR phase. Dynamic mechanical spectra showed that the PP-b-EPR block
copolymers are incorporated into the PP phase, and consequently, the EPR portions of the block are trapped into the interlamellae of PP.
䉷 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Polypropylene; Ethylene–propylene random copolymer; Rheo-optics

1. Introduction metry (DSC), 13C NMR, gel permeation chromatography

(GPC), optical microscopy, and cross fractionation chroma-
Much attention has been paid to blends of isotactic tography (CFC).
polypropylene (PP) and olefin elastomers such as ethy- The present work deals with the changes in morphology
lene–propylene random block copolymer (EPR) for the and dynamic mechanical spectrum of PP/EPR binary blends
sake of both scientific interest and commercial utility in on the addition of a PP-b-EPR block copolymer as well as
the past two decades [1]. PP/EPR blends have been inves- their effects on tensile mechanical properties.
tigated with the aim of improving impact behavior. A lot of
effort is still being made to further improve the mechanical
properties and morphology of these blends and to expand 2. Experimental
their applicability. In such circumstances, the additive effect
of a third polymer such as diblock copolymers of PP and 2.1. Materials and blend preparation
EPR (PP-b-EPR) is of very scientific and practical interest
[2,3]. Two commercial grades of isotactic polypropylene (hPP
We have succeeded in synthesizing a complete diblock and rPP) and also a commercial grade of ethylene–propy-
copolymer of PP and EPR (PP-b-EPR) with a short-period lene rubber (EPR) supplied by TOSOH Corp. were used in
polymerization technique [4,5]. It is well-known that the this study. The hPP is a homopolymer and rPP is a random
short-period (or stopped-flow) polymerization makes it block copolymer with 3.2 wt% ethylene. The diblock
possible to perform “quasi-living polymerization” during a copolymers of PP and EPR (PP-b-EPR) were synthesized
very short period (up to about 0.2 s) in such a way as to by a short-period polymerization method with a MgCl2-
avoid a chain transfer reaction [6,7]. In the previous articles supported Ziegler catalyst in toluene at 303 K. The block
[4,5,8], the block formation of the PP-b-EPR copolymer was composition of PP-b-EPR was controlled by changing the
thoroughly examined using differential scanning calori- polymerization times. In this work, the additive effects of a
block copolymer PP-b-EPR(50–50), in which the numerals
represent the weight fraction in percentage of the PP and
* Corresponding author. Tel.: ⫹ 81-761-51-1621; fax: ⫹ 81-761-1625. EPR parts, were investigated. For comparison, the PP-b-
E-mail address: nitta@jaist.ac.jp (K. Nitta). EPR(75–25) block was used only for some measurements
0032-3861/00/$ - see front matter 䉷 2000 Elsevier Science Ltd. All rights reserved.
PII: S0032-386 1(99)00895-2
6766 K. Nitta et al. / Polymer 41 (2000) 6765–6771

Table 1
Characterization of polymers

Polymers Composition (%) Mw × 10 ⫺4a Mw/Mn a Ethylene b content Tm c (K) Density Crystal form d
(mol%) (kg m ⫺3)
PP EPR

hPP 100 0 26 5.7 – 438 909 Monoclini

rPP 100 0 25 6.0 5.4 421 900 Monoclinic
EPR 0 100 11 1.7 63 – 853 –
PP-b-EPR(75–25) 75 25 5.1 3.2 17 434 899 Monoclinic
PP-b-EPR(50–50) 50 50 4.2 3.0 26 433 892 Monoclinic
a
Determined by gel permeation chromatography, PP standard.
b
Determinied by 13C NMR.
c
Melting temperature determined by DSC.
d
Determined by wide angle X-ray diffraction.

of dynamic mechanical properties. Details of the polymer- with a transmission electron microscope model HITACHI
ization procedure were shown in the previous paper [4]. H-7100. The ultrathin films were sectioned into slices of
Their molecular characteristics are summarized in Table 100 nm thickness with an ultramicrotome (Reichert-Nissei
1. The molecular weight and its distribution were deter- ULTRACUTS) at 133 K. It should be noted that the mole-
mined using a high temperature GPC instrument (Senshu cular weight of PP-b-EPR is much smaller than that of these
SSC-7100) with o-dichlorobenzene as a solvent at 313 K. commercial PPs and EPR polymers. The ultrathin films
The ethylene content in the samples was determined by 13C were then stained with ruthenium tetraoxide for 12 to
NMR spectra using a Varian Gemini-300 spectrometer. 24 h. Photographic contrast is produced by selective elec-
Various blend polymers such as binary PP/EPR and tern- tron scattering from the stained non-crystalline phase.
ary PP/EPR/PP-b-EPR blends were prepared in a solution of The measurements of the linear dynamic mechanical
xylene at 413 K. The blend polymers were precipitated from properties were made using a dynamic mechanical analyzer
the solution into methyl alcohol and then dried in a vacuum (Rheology DVE-V4) on film specimens of the following
oven at 333 K and for 10 h. dimensions: length 20 mm, width 5 mm, and thickness
0.3 mm. The dynamic tensile moduli, the storage modulus
2.2. Sample preparation and characterization E 0 , the loss modulus E 00 , and the loss tangent tan d ˆ E 00 =E 0 †
were measured between 120 and 430 K at a constant
The samples were melt pressed in a laboratory hot
frequency of 10 Hz and a heating rate of 2 K/min.
press at 463 K and at 12 MPa. The film specimens were
Stress–strain behavior in the uniaxial tension was
prepared by quenching from the melts into an ice-water
measured using a Shimadzu AGS-5 kN. The sample
bath. The results of the film characterization were also
specimens were cut with a dumbbell shape in which the
included in Table 1.
gauge length is 10 mm. The tensile strain was calculated
DSC measurements were carried out using a Mettler
from the ratio of the increment of the length between
Tredo calorimeter DSC820 that was calibrated for tempera-
clamps to the initial gauge length. The tensile stress
ture and melting enthalpy using indium as a standard. The
was determined by dividing the tensile load by the
samples of about 10 mg weight sealed in aluminum pans
initial cross section. The stress–strain curves at 298 K
were used for the measurements. The samples were heated
were measured at a constant cross-head speed of 5, 10, 20,
from 170 to 500 K at a scanning rate of 10 K/min under a
and 50 mm/min. The tensile strain was calculated from the
nitrogen atmosphere.
ratio of the increment of the length between clamps to the
The crystal form of the films was examined by wide-
initial gauge length.
angle X ray diffraction (WAXD). The measurements were
In order to examine the orientation behavior of PP crys-
carried out with at a scanning speed of 1⬚/min over a 2u
tals (c-axis) for the present samples, we measured the infra-
range from 8 to 40⬚ using a WAXD instrument (Rigaku
red dichroism of the 998 cm ⫺1 band simultaneously with the
RINT-2000).
tensile load during elongation. Details of these experimental
Densities of the films were determined by a floatation
procedures were presented in the previous study [9]. Here,
method. The binary medium prepared from various ratios
we briefly repeat the main outlines.
of distilled water and ethyl alcohol was used.
A tensile tester was placed in a Fourier-transform
2.3. Measurements infrared (FTIR) spectrometer (JASCO FT-IR500) in
such a way as to allow the infrared beam to pass a
The overall morphology of the blend films was examined central point on the film mounted on the tensile tester.
 K. Nitta et al. / Polymer 41 (2000) 6765–6771 6767

Fig. 2. TEM micrographs of thin sections for (a) the addition of 20 wt% of
PP-b-EPR(50–50) to hPP homopolymer; (b) the addition of 20 wt% of PP-
b-EPR(50–50) to EPR copolymer.

3. Results and discussion

3.1. Morphology

TEM micrographs for the typical film specimens are

exemplified in Figs. 1 and 2, in which the dark regions
correspond to the stained EPR rich phase, whereas bright
regions correspond to the crystalline PP rich phase. The PP-
b-EPR(50–50) block film exhibits a homogeneous morphol-
ogy (Fig. 1a), whereas the rPP/EPR(50/50) blend exhibits a
bicontinuous phase separation (Fig. 1b). The TEM micro-
Fig. 1. TEM micrographs of thin sections for (a) PP-b-EPR(50–50) diblock; graphs of the rPP/EPR blends were very similar to those of
(b) rPP/EPR(50/50) blend; and (c) the addition of 20 wt% of PP-b-EPR(50– the hPP/EPR blends. As shown in Fig. 1c, the addition of
50) to rPP/EPR(50/50) blend. 20 wt% of PP-b-EPR(50–50) into the binary rPP/EPR(50/
50) blend causes a change in domain size of EPR, in which
the EPR phase appears to be completely surrounded by the
The tensile tester was designed with upper and lower PP phase, although the content of EPR in the blends does not
clamps to symmetrically move from the central point or the change with the addition of PP-b-EPR. Based on the fact
beam point on the film. The cross-head speed was 1 mm/ that the PP phase was enlarged, one may infer that the
min in all cases. majority of the PP-b-EPR is embedded in the PP phase.
6768 K. Nitta et al. / Polymer 41 (2000) 6765–6771

Fig. 4. Compositional dependence of the glass transition temperatures of PP

and EPR for the addition of PP-b-EPR(50–50) to PP/EPR(50/50) blend.

ture dependences of E 00 in the glass-relaxation region are

shown. As seen in these figures, the higher temperature peak
is ascribed to the Tg of the amorphous region of PP, and the
lower relaxation peak is to the Tg of the EPR component. It
was found that the Tg of PP is shifted to a lower temperature
on adding PP-b-EPR, whereas the Tg of the EPR component
does not change with the addition of PP-b-EPR. Fig. 4
summarizes the additive effect of PP-b-EPR(50–50) on
the two Tgs of PP/EPR(50/50) blends. This strongly suggests
that the PP-b-EPR molecules are incorporated into PP
phase, resulting in trapping the EPR portions of the
PP-b-EPR into the interlamellar regions of PP. The

Fig. 3. Temperature dependence of the mechanical storage modulus (E 0 ),

loss modulus (E 00 ) and loss tangent (tan d ) with temperature for (a) rPP/
EPR(50/50) blend and the addition of 20 wt% of PP-b-EPR(50–50) to rPP/
EPR(50/50); and (b) hPP/EPR(50/50) blend and the addition of 20 wt% of
PP-b-EPR(50–50) to hPP/EPR(50/50).

Fig. 2 compares the morphological features of 50 wt%

addition of the PP-b-EPR to the hPP and EPR polymers.
The morphology of the blend with EPR is clearly different
from that of the blend with PP. The PP/PP-b-EPR exhibits a
homogeneous, morphology whereas the PP domains are
dispersed into the EPR matrix in the EPR/PP-b-EPR sample.
This suggests that the PP-b-EPR block copolymer is compa-
tible with PP but incompatible with EPR.

3.2. Dynamic mechanical properties

Fig. 3a and b show the effects of 20 wt% addition of the Fig. 5. Temperature dependence of the mechanical storage modulus (E 0 ),
PP-b-EPR(50–50) block on the dynamic mechanical beha- loss modulus (E 00 ) and loss tangent (tan d ) with temperature for (W) hPP
vior of the PP/EPR(50/50) blends. In these figures, tempera- and (X) binary (50/50) blend of hPP and PP-b-EPR(50–50).
 K. Nitta et al. / Polymer 41 (2000) 6765–6771 6769

Fig. 8. Additive effect of PP-b-EPR(50–50) to hPP/EPR(50/50) blend on

stress–strain behavior at 298 K and 20 mm/min.

component is trapped in the amorphous region of PP

consistent with the finding that the PP/PP-b-EPR blend
Fig. 6. Temperature dependence of the mechanical storage modulus (E 0 ), shows no phase separation in the TEM micrograph (see
loss modulus (E 00 ) and loss tangent (tan d ) with temperature for (W) PP-b-
Fig. 2a). Also, the addition of PP-b-EPR to PP causes a
EPR(75–25) diblock and (X) binary (50/50) blend of hPP and PP-b-
EPR(50–50). reduction in the dynamic moduli of PP over the entire
temperature range. Fig. 6 compares the dynamic mechanical
spectra of a PP-b-EPR(75–25) block sample containing the
morphological features in the TEM observation are in same EPR content with the PP/PP-b-EPR(50/50) blend. The
agreement with the dynamic mechanical behavior of the overall spectrum of PP/PP-b-EPR is found to be almost
PP/EPR/PP-b-EPR ternary blends. the same as that of its corresponding block copolymer,
The addition of an amount (50 wt%) of PP-b-EPR(50– although the PP-b-EPR(75–25) block sample manifests a
50) to the PP homopolymer affects the dynamic mechanical slightly lower Tg.
spectra. As shown in Fig. 5, the mechanical loss peak corre- Fig. 7 shows the effect of adding 50 wt% of the PP-b-
sponding to Tg in the PP/PP-b-EPR(50/50) blend is broa- EPR(50–50) block into the EPR copolymer on the dynamic
dened and shifted down in temperature relative to that of the mechanical relaxation process. For comparison, the
PP homopolymer. This result also suggests that the EPR dynamic mechanical spectrum of PP-b-EPR(50–50) is
included in the figure. As shown in Fig. 7, the EPR/PP-b-
EPR blend shows two dispersion peaks which are located at
the Tgs of EPR and PP-b-EPR(50–50), suggesting that PP-b-
EPR is immiscible with EPR. This may be due to the fact
that the ethyl content or molecular mass of the EPR portions
of PP-b-EPR is different from that of EPR. This result is
consistent with the finding that the EPR/PP-b-EPR blends

Fig. 7. Temperature dependence of the mechanical storage modulus (E 0 ),

loss modulus (E 00 ) and loss tangent (tan d ) with temperature for (K) EPR,
(W) PP-b-EPR(50–50) diblock, and (X) binary (50/50) blend of EPR and Fig. 9. Additive effect of PP-b-EPR(50–50) to rPP/EPR(50/50) blend on
PP-b-EPR(50–50). stress–strain behavior at 298 K and 20 mm/min.
6770 K. Nitta et al. / Polymer 41 (2000) 6765–6771

discontinuity of EPR phases leads to a brittle nature. The

superiority of the former effect over the latter effect for such
multiphase polymers is sensitive to the structural feature of
their components, phase continuity, and morphology
conversion. It is indicated that the effect of lowering the
Tg of PP is superior to the dispersion effect of EPR in the
case of the addition of 10 wt% PP-b-EPR to rPP/EPR.

3.4. Deformation mechanism

In order to examine the orientation behavior of PP

crystals during tensile deformation, we measured the
dichroism ratio of the 998 cm ⫺1 band simultaneously
with the stress–strain curve. As shown in Fig. 10, the
rPP/EPR(50/50) and hPP/EPR(50/50) blends showed no
well-defined yield points, and the both blends were elon-
gated without orientation of the PP chains. On the other
hand, as shown in Fig. 11, the addition of PP-b-EPR
copolymer induces orientation of PP chains and this
leads to a yield point. This is plausible since the stress
concentration occurs on the PP phase because of the
discontinuity of the EPR domains.
It is interesting to note that the 20 wt% addition of the PP-
b-EPR(50–50) to the rPP/EPR(50/50) blends induces orien-
tation of PP, whereas the orientation function of PP crystals
for hPP/EPR/PP-b-EPR shows a great decrease and then
increases after passing a minimum around 50% strain.
There is a great difference in the additive effects of PP-b-
EPR between rPP/EPR and hPP/EPR on the deformation
mechanism. This will be due to the fact that the lamellar
orientation and rotation forced by the external load causes
the chain axis in the PP crystals (c-axis) to orient perpendi-
cular to the stretching direction. The further elongation
Fig. 10. Strain dependence of orientation function for 998 cm ⫺1 band of (a)
rPP/EPR(50/50) blend and (b) hPP/EPR(50/50) blend. induces the lamellar fragmentation and this can lead to the
orientation of the c-axis becoming progressively greater
with increasing strain. In the case of rPP/EPR/PP-b-EPR,
the lamellar fragmentation occurs more easily in the rPP
shows a phase-separated morphology and that the bright
lamellae with additional defects due to the comonomer
regions are completely surrounded by EPR regions (see
(ethylene) units [10]. Therefore, the orientation function
Fig. 2b).
of the c-axis increases immediately. Moreover, the differ-
ence in the tensile behavior between rPP/EPR/PP-b-EPR
3.3. Tensile mechanical properties and hPP/EPR/PP-b-EPR, as described in the previous
section, may be related to the difference in their deformation
The addition of the PP-b-EPR(50–50) to PP/EPR(50/50)
mechanisms. More research is necessary to elucidate the
blends strongly modifies the overall stress–strain behavior
negative and positive orientation behaviors of these tertiary
as exemplified in Figs. 8 and 9. It was found that the stress or
blends.
yield stress increases with increasing PP-b-EPR content,
whereas the addition of the PP-b-EPR to hPP/EPR blends
causes a drastic reduction in the elongation at break. In the 4. Conclusions
case of rPP/EPR, however, the largest value of elongation at
break is found for the blend with 10 wt% PP-b-EPR. The The results presented show that the PP-b-EPR(50–50)
similar tendency was confirmed under different elongational block copolymer is incompatible with the EPR copolymer
conditions. but compatible with isotactic PP polymers. A homopolymer
It was found from the present study that the addition of (hPP) and a random block copolymer with 3.2 wt% ethylene
PP-b-EPR induces not only a lowered Tg of PP but also the (rPP) exhibited essentially similar compatibility. Thus, it
discontinuity of the EPR phase. The effect of the lowered Tg was found that the majority of the PP-b-EPR copolymer is
of PP leads to ductility; on the contrary, the effect of the incorporated into the PP phase in the PP/EPR blends, and
 K. Nitta et al. / Polymer 41 (2000) 6765–6771 6771

blend and the glass transition temperature and moreover,

affects their tensile mechanical properties. Although the
chemical structure of these copolymers is of an intermediate
nature between PP and EPR, they cannot always act as
“compatibilizing agents” between the amorphous region
of PP and the EPR phase. This means that a better homo-
genization failed to be achieved with the addition of the PP-
b-EPR(50–50) block. This may be due to the fact that the PP
portions in the PP-b-EPR(50–50) block possibly cocrystal-
lized with PP molecules during the melt-crystallization
process because the PP-b-EPR molecule has the potential
to possess a higher mobility resulting from its considerably
lower molecular weight compared with pure PP or EPR
polymers.
It is of very interest to note that there is a quite difference
in the additive effects of PP-b-EPR between rPP/EPR and
hPP/EPR on the PP crystal orientation process during a
elongation. Thus, it was found that the rPP/EPR/PP-b-
EPR shows the orientation of PP crystals (c-axis) in the
parallel direction to the elongation, whereas hPP/EPR/PP-
b-EPR shows the orientation of PP crystals (c-axis) in the
perpendicular direction. In future, details of molecular
mechanism for the orientation behavior of PP crystals will
be studied.

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