Classification: Internal Use
Effect of nucleating agent on properties of in-situ copolymer polypropylene and PP/POE
Blends
Mansour N. Al-Otaibi and Saeed Al-Zahrani
King Saud University, Department of Chemical Engineering, Riyadh, KSA
Abstract
Toughening of homopolymer polypropylene
(PPH) in the post reactor step by incorporating external
elastomers has become an attractive area of research. In this
investigative work, PPH was post-reactor blended with
different types of Polyolefin elastomers (POE) that were
selected based on the co-monomer type and density. The
performance behavior of PPH/POE blends with and
without a nucleating agent was compared to in situ (in the
reactor) modified PPH with Ethylene Propylene Rubber
(EPR). The addition of POE in PPH, increased toughness
at room temperature and the stiffness of the blends
decreased. The addition of a nucleating agent was noted to
improve the toughness and stiffness compared to their non-
nucleated counterparts, while the tensile strength remained
unchanged. At -20 °C, the impact strength results showed
no significant improvement in PPH/POE blends with and
without addition of the nucleating agent. The melting
temperature and the crystallinity of PPH matrix decreased
and the crystallization temperature remained unchanged.
On the other hand, the nucleating agent has kept the melting
temperature unchanged and increased the crystallinity and
crystallization temperature of the blends. The morphology
analysis have shown clearly the phase separation of the
blends components thus demonstrating the immiscibility of
the blend system. The addition of the nucleating agent was
seen to decrease the domain size of POE phase thus leading
to the improvement in the toughness properties of the
blends. ICP materials have shown better mechanical
properties and more uniform rubber dispersion than the
blends system.
Introduction
Polypropylene is one of the most important
thermoplastic materials used in a wide variety of
application such as packaging, consumer goods, building,
and automotive in view of its easy processing, low density,
chemical resistance, and low cost. At low temperatures, the
applications of PP are limited due its low impact resistance
(1,2). To remedy this problem, a new family of
polypropylene known as Impact PP was developed by
incorporating a rubber phase (EPR) in the reactor (in situ
modification). The process of producing impact copolymer
polypropylene in situ takes place in two stages. In the first
one, the homopolymer polypropylene is produced in the
first reactor and in the second stage, ethylene-propylene
rubber (EPR) is produced in presence of the homopolymer
polypropylene in the second reactor (3). However,
incorporation of an elastomer (EPR, EPDM, and POE) by
blending with homopolymer polypropylene outside the
reactor is also used as a method to improve the impact
resistance of PP materials (3-7).
Many research groups have studied the effect of
incorporating ethylene-alpha olefin in polypropylene
(Homopolymer, Random copolymer, impact copolymer)
on the mechanical properties. T. McNally et al [8] they
used Ethylene-octene copolymer blended in homopolymer
polypropylene and found that the tensile modulus and
flexural strength decreased as the POE content was
increased. In another work carried out by Tang, W. et al.
[9], noted that the POE acts as nucleating agent when
incorporated in random polypropylene matrix.
Incorporating the nucleating agents in PP/POE blends were
also the subject of several research works. Nucleating
agents are known to increase the number of crystallization
sites in semi-crystalline polymers, resulting in an increase
in overall crystallization rate, a decrease in the spherulite
size and an increase in crystallization temperature thus
decreasing the production cycle time during polymer
conversion. In addition, the nucleating agents are known to
not affect impact strength (in general), tensile strength,
flexural modulus, and clarity. Xiangfu, Z., et al. (10) have
used sorbitol nucleating agents in PP/POE blends and
found that with the addition of nucleating agents the
stiffness and toughness increased simultaneously at the
same content of POE and better balance between stiffness
and toughness was reached compared to non-nucleated
blends.
The purpose of this work was to study the effect of
nucleating agent incorporation on the blends properties and
compare the morphology and toughness/stiffness balance
properties of PPH blended with different types of POE
(different co-monomer / different density) to those of its
counterpart from in situ reactor blends known as impact PP.
Materials and Testing
A commercial homopolymer polypropylene (PPH)
and impact polypropylene (ICP) (Melt Flow Index (MFI):
25 g/10 min for PPH and 21 g/10 min for ICP). The above
mentioned PPH was used as a matrix resin for the blends.
On the other hand, the impact polypropylene (ICP) with
total rubber content around 15% was used as benchmark
for the PPH/POE blends performance investigation.
Classification: Internal Use
Different types of POE’s were used as impact modifier
depending on their co-monomer type, density, and melt
index. Alpha nucleating agent was used with dosage of 300
ppm in the polymer formulations. Table 1 show the
polymers used in this work with melt index, density, and
co-monomer types.
In this work, PPH/POE Blends were prepared with and
without a nucleating agent. Also the POE content in the
blends system was selected as 10, 15, and 20 wt. %. The
compounding work was carried out on a KraussMaffei co-
rotating twin-screw extruder. The screw diameter of the
latter was 25 mm with an L/D of 56. The screw speed and
the cutter speed were 500 rpm and 2800 rpm respectively.
The palletization step was done using an underwater cutter
at a water temperature of 40°C. Flexural and izod impact
test specimens were prepared using KraussMaffei
KM50/380 EX injection molding with a 30 mm screw
diameter and 26.7:1 L/D ratio.
Flexural test was performed according to ASTM 790
using (Zwick/Roell Z010) with a compression load cell at
constant crosshead speed 1.36 mm/min.
Notched izod impact tests were done according to
ASTM D256 at room temperature (23 °C) and below zero
at -20 °C using Zwick/Roell HIT50P pendulum type impact
tester. The dimensions of test bar is (64 × 12.7 × 3.2 mm),
notched depth is 10.2 mm, and the notched type is A.
A differential scanning calorimeter (DSC), model
DSC-Q2000cwas used to study the thermal properties of
the PP/POE blends. About 5-7 mg of samples was
accurately weighted and encapsulated in a typical
aluminum pan. An empty sealed pan was used as a
reference. All the DSC tests were conducted in nitrogen
environment because we want see the melting and
crystallization. The samples were heated with a constant
rate of 10 °C/min from 50 °C to 195 °C (1st heating scan)
and held for 5 min to erase their thermal history and to
permit complete melting of the previous crystals.
Subsequently, samples were cooled down to 50 °C at a
constant rate of -10 °C/min (cooling scan) to study the
crystallization behavior. Finally, the samples were heated
again for the second time (2nd heating scan) at 10 °C/min
to 195 °C to find the melting temperature of each sample.
The morphologies of the blends were analysis from
molded sheet bars using scanning electron microscope
(SEM-FEI Quanta 200) at an accelerating voltage of 20 kV.
The cryo-fractured surface of each specimen was etched by
xylene at room temperature for 15h in order to remove the
rubber phase. Then, the specimens were dried and coated
with a thin layer of gold.
Discussion
Flexural modulus data presented in Figure 1 and 2, it
can be noted that the modulus of the PPH/POE blends
decreased upon the incorporation of the elastomer phase.
This was expected due to the incorporation of soft particles
(dispersed POE phase) which have lower elastic modulus
than that of the matrix PPH and due to the lowering of the
crystallinity of the latter same observation was reported in
literature (7, 11, 12). The ICP material presented a
marginally higher flexural modulus compared to its
counterparts based on PPH/POE blends with 15%
elastomer content. This could be attributed to the better
compatibility of the PPH/EPR in ICP as compared to
PPH/POE system coupled to higher crystallinity of the PPH
matrix in presence of the EPR phases. The effect of the
incorporated nucleating agent was seen to improve the
flexural modulus of all blend systems as compared to their
non-nucleated blends counterparts and this could be related
to the fact that the nucleating agent reduces the spherulite
size of the polymer crystals (10, 13), reduces their size
distribution (improvement in spherulites homogeneity),
and increase slightly the crystallinity of the blend. The
nucleated ICP sample have presented noticeably higher
flexural moduli values than PPH/POE blends with 15%.
loading of POE. This is related to the better compatibility
of PPH/EPR in ICP as compared to PPH/POE systems and
increase in crystallinity of the matrix phase.
The Notched Izod impact results of PPH, PPH/POE
blends, and ICP in presence and absence of the nucleating
agent are summarized in Figures (3 – 6). It is clearly seen
the noticeable improvement in impact strength with
increase of the POE content at room temperature. On the
other hand, the ICP presented superior impact properties
compared to PPH/POE blends at the same level of
elastomer content (15%). Therefore, it can be deduced that
EPR introduced in polypropylene during the in-situ
polymerization (ICP) is more effective in improving the
impact strength of PPH than POE copolymers introduced
during post- reactor compounding. This is most probably
related to the better dispersion and compatibility of right
particle size and size distribution of the EPR phase in ICP
systems as compared to their compounded PPH/POE
equivalents. The addition of the nucleating agent to
PPH/POE blends was seen to improve the notched izod
impact of the systems that could be related to the reduction
of the PPH matrix spherulite sizes and increase in their size
homogeneity. It is important to note also from the test
results that POE based on butene co-monomer (POE1 and
POE2) imparted higher impact values to POE based on
octene co-monomer (POE3 and POE4) in presence of the
nucleating agent and this could be attributed to the
copolymer chemical structure (co-monomer content, co-
monomer distribution, branching size) and also to its higher
MFI that might have imparted lower PPH/POE viscosity
ratio (7, 10, 14-15). At -20 °C, the impact strength results
showed no significant improvement in PPH/POE blends
with and without addition of the nucleating agent and this
could be due to the ductile-brittle transition-taking place at
this temperature. On the other hand, the ICP impact
strength values, with and without nucleating agent were
shown to be superior at low temperature (-20 °C) compared
to the blends PPH/POE. This could be related to the fact
that the EPR phase in ICP possess better ductility and
toughness than POE particles.
Classification: Internal Use
From the Differential Scanning Calorimetry (DSC)
analysis results presented in Table 2 on PPH, PPH/POE
blends, and ICP in presence and absence of the nucleator,
it was noted that a gradual, small decrease in melting
temperatures of the blends (no preference for any POE
copolymer) with increasing elastomer content took place.
However, this effect was not noted in systems containing
the nucleating agent where the melting point of the systems
remained unchanged. It is worth noting also that the
crystallization temperature was seen not to be affected in
nucleated and non- nucleated blends by the incorporation
of the elastomer phase, POE or EPR. This could be seen as
that the elastomer phase tend to disturb the packing order
of the PPH polymer chains and slightly interfering with the
crystallization behavior of the host matrix. The crystallinity
content improvement in the blend systems in the presence
of the nucleating agent is possibly related to the high
number and lower size of the PP matrix spherulites
developed during cooling.
From the SEM micrographs, it is observed that all
blends presented continuous and dispersed phases based on
PPH and POE respectively. This is a classical morphology
of an immiscible system at all blend ratios. The SEM
micrographs of blends system with butene based POE
(POE1 and POE2) (figure 9) have shown that the dispersed
phase was finer than that present in blends based on octene
POE (POE3 and POE4). This could be due to the better
compatibility of the butene-based copolymers with the
PPH matrix as reported by some researchers that butene
and hexene copolymers are miscible in the amorphous
phase of PPH matrix (16). It is also worth noting that
copolymers with the highest MFI values (lower viscosity)
have imparted the finest dispersed phase in the blends
investigated. This is probably due the fact that the
homopolymer phase will encounter less resistance in
breaking up the lower viscosity dispersed phase during
compounding and moulding (high shearing at the gate). In
blends with highest POE contents (exception for blend with
POE4 it was observed that at 20% POE content some
elongated dispersed particles were formed and this could
be due to particles coalescence (17). In ICP polymer it was
observed that the EPR dispersed phase was more
homogeneous in size and shape (round) and was in between
the phase sizes developed in butene based POE (POE1 and
POE2) and octene based POE (POE3 and POE4)
copolymer based blends. This is mainly related to the better
compatibility of the EPR copolymer with PPH and possibly
to the right viscosity ratio of the PPH/EPR system
compared to PPH/POE counterparts. From the impact test
results and morphology analysis, it can be concluded that
the dispersed particles morphology and size in ICP polymer
is most effective in toughening the PPH matrix. Addition
of a nucleating agent to ICP and PPH/POE blends was
observed to modify the morphology of the dispersed phase
in some PPH/POE blends. In the SEM micrographs ( refer
to figure 10), it can be seen that the dispersed phase in
blends based on POE1, POE2 and POE3, presented highly
elongated or fibrillary shape, while in POE4 based blend
the dispersed particles were oval. However, in ICP polymer
the EPR phase is round and similar in morphology to its
counterpart in ICP without the nucleating agent. These
morphologies could be explained by the fact that the lower
viscosity copolymers, POE1, POE2 and POE3 have
developed elongated morphologies during samples
moulding (shear induced particles orientation and
stretching) using injection moulding followed by
subsequent faster cooling in the mould under the influence
of the nucleating agent (faster crystallization or high
undercooling). This effect was not observed in ICP material
and POE4 copolymer based blends, probably due to the
difficulty in stretching and freezing the high viscosity
dispersed phase. It is important to mention here that the
improvement in impact strength at 23 °C of the nucleated
samples based on POE1, POE2 could have been due to the
formation of the fibrillar-dispersed phase, coupled to its
better compatibility with PPH matrix.
Conclusions
 Flexural modulus decreased with increasing the POE
content in PPH in the presence and absence of nucleating
agent. The ICP material presented a marginally higher
flexural modulus compared to its counterparts based on
PPH/POE blends with 15% elastomer content.
 The in-situ polymerization (ICP) is more effective in
improving the impact strength at low temperature than
PPH/POE blends introduced during post- reactor
compounding.
 No significant of effect on the melting and crystallization
temperature due to the addition of POEs and EPR.
 The morphological investigation indicated that all
PPH/POE blends and ICP system were immiscible in the
ratios investigated.
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Classification: Internal Use

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APPENDIX
Table 1: Polymers used in this work with melt index, density, and co-monomer types.
Polymer MFR ( g/10min @ 230 °C, 2.16 kg) Density (kg/m3) Co-polymer type
PPH 24 906 -
POE1 2.5 862 C2-C4
POE2 7.25 870 C2-C4
POE3 1.85 885 C2-C8
POE4 0.823 868 C2-C8
ICP 21 905 In-situ modified

Figure 1. Flexural modulus for non-nucleated PPH/POE blends. Figure 2. Flexural modulus for nucleated PPH/POE blends.
Classification: Internal Use

Figure 3. Izod impact at RT for non-nucleated PPH/POE blends. Figure 4. Izod impact at RT for nucleated PPH/POE blends.

Figure 5. Izod impact at -20 °C for non-nucleated PPH/POE blends. Figure 6. Izod impact at -20 °C for nucleated PPH/POE blends.

Table 2. Melting temperature, crystallization temperature, and crystallinity of blends.

Melting temperature Crystallization temperature
Crystallinity %
Sample Rubber (°C) (°C)
Name content % without with without with without with
nucleator nucleator nucleator nucleator nucleator nucleator
PPH 0% 164.30 164.6 113.15 130.1 44.28 48.915
10% 162.9 164.1 113.75 129.2 41.885 46.33
POE1 15% 163.7 163.6 113.45 128.3 39.01 44.76
20% 161.6 163.7 113.65 127.7 44.905 40.63
10% 164.1 164.4 113.25 129.35 40.58 46.55
POE2 15% 163.1 164 113.4 129.4 40.815 43.765
20% 161.6 164.1 113.25 128.95 39.08 39.255
10% 162 163.9 114.35 129.95 42.15 46.815
POE3 15% 162.1 164 114.3 129.95 39.275 43.915
20% 162.4 164 113.65 129.5 38.91 42.035
10% 162.2 164.4 114.55 129 43.965 44.345
POE4 15% 163 163.8 114.6 129.2 41.86 43.36
20% 161 164.3 114.75 128.65 39.105 40.015
ICP 15% 165.6 165.1 118 130 43.88 45.27
Classification: Internal Use

POE1 POE2 POE3

POE4 ICP

Figure 7. SEM images for fractured and etched surfaces of 15% POE for non-nucleated blends.

POE1 POE2 POE3

POE4 ICP

Figure 8. SEM images for fractured and etched surfaces of 15% POE for nucleated blends.