Polymer Blends Based On Polyolefin Elastomer and PP PDF
Polymer Blends Based On Polyolefin Elastomer and PP PDF
Polymer Blends Based On Polyolefin Elastomer and PP PDF
Polypropylene
ANA LÚCIA N. DA SILVA, 1 MARIA INÊS B. TAVARES, 1 DANIEL P. POLITANO, 1 FERNANDA M. B. COUTINHO, 1
MARISA C. G. ROCHA 2
1
Instituto de Macromoléculas Professora Eloisa Mano, UFRJ, P.O. Box 68525, 21945–970, Rio de Janeiro, RJ, Brasil
2
Instituto Politécnico, Campus Regional da UERJ, Nova Friburgo, RJ, Brasil
ABSTRACT: A new family of homogeneous polyolefin polymers that exhibit unique mo-
lecular and rheological properties designated polyolefin elastomers (POEs) are charac-
terized by a narrow molecular weight and high degrees of comonomer distribution.
Because these copolymers are often elastomeric in nature, one of the uses for these
materials is as impact properties improver for brittle polymers such as polypropylene
at low temperatures. In this work a study was carried out about the effectiveness of
the polyethylene elastomer (POE) as an impact modifier for polypropylene in relation
to the traditional modifier EPDM. In this study the flow properties of of the POE/PP
and EPDM/PP blends were also evaluated. The blends were analyzed by solid-state
13
C nuclear magnetic resonance ( 13C-NMR) spectroscopy, scanning electron microscopy
(SEM), and differential scanning calorimetry (DSC). The results showed that PEE/
PP and EPDM/PP blends present a similar crystalline behavior, which resulted in a
similar mechanical performance of the blends, on the composition analyzed. It was also
verified that the POE/PP blend presents lower torque values than the EPDM/PP blend,
which indicates a better processability when POE is used as an impact modifier. q 1997
John Wiley & Sons, Inc. J Appl Polym Sci 66: 2005–2014, 1997
2005
ene–diene terpolymers (EPDM) have been consid- Dow Chemical, known as ENGAGE polyolefin
ered the most effective ones.4,5 elastomers (POEs), has been commercialized. En-
Recent catalyst developments in polyolefin gage POEs (ú20 wt % octene comonomer) have
synthesis allowed the control of molecular distinctive properties when compared with elasto-
weight distribution and the proportion of como- meric materials currently available, due to the
nomer incorporation. Those emerging catalyst long chain branching. POEs are aimed for compet-
systems, termed single-site catalysts ( metallo- ing with thermoplastic olefin impact modifiers,
cene type ) , allow polymer producers to make a like EPDM.8,9
much more well-defined molecule by enabling According to the manufacturer, POEs can com-
the incorporation of long comonomer chains.6 pete against ethylene–propylene–diene terpo-
The metallocene catalysts are having a tre- lymers (EPDM) in the production of polypropyl-
mendous impact on the polyolefin industry. In ene-based blends because of their pellet form,
contrast with the conventional heterogeneous which allows for faster mixing and expanded han-
Ziegler-Natta catalysts ( multisite ) , the single- dling and compounding option.10
site catalyst leads to a higher degree of como- Thus, the aim of this work is to evaluate the
nomer incorporation, while the uniform reactiv- effectiveness of the new polyethylene elastomer
ity allows the synthesis of very homogeneous (PEE) as an impact modifier for polypropylene
copolymers.7 and verify if this new polymer can replace the
One family of these new polymers produced by conventional impact modifier—EPDM.
Figure 2 Torque curves of the EPDM/PP blend, the PEE/PP blend, and PP.
Figure 3 Total torque curves of the EPDM/PP blend, the PEE/PP blend, and PP.
MFI
Material (g/10 min)
PP 2.1 { 0.5
PEE/PP 2.0 { 0
EPDM/PP 1.3 { 0
DH r Crystallinity
Sample (J/g) (wt %)
PP 90.0 43
PEE/PP 60.9 29
Figure 4 Melting behavior of the pure polymers and
EPDM/PP 63.0 30
PP blends.
Table IV Glass Transition Temperature of PP torque’’ characterizes the viscous nature of the
and PP Blends melt.
It can be seen (Fig. 1) that the polyethylene
Material Tg1 (7C) Tg2 (7C) elastomer (PEE) has a lower value of torque than
EPDM. This behavior means that PEE has a bet-
PP 05 —
PEE 047 —
ter response during processing than EPDM. It
EPDM 042 — also indicates that the PEE melt viscosity, at the
PEE/PP 054 03 shear rate and temperature employed, is closer to
EPDM/PP 047 05 the PP viscosity.
The torque versus time curves of PEE/PP and
EPDM/PP blends (Fig. 2) show that the PEE/
PP blend presents lower torque values than the
MHz and 75.4 MHz for 1H and 13C, respectively. EPDM/PP blend. These results indicate that a
All experiments were carried out at ambient
better processability of the blend should be ex-
probe temperature and were performed using pected when the polyethylene elastomer is used
gated high-power decoupling. Zirconium oxide ro- as a PP impact modifier.
tor of 7 mm diameter with Kel-F caps were used
The area under the curve result of the plot total
to acquire the NMR spectra at rates of 4 kHz.
torque versus time gives the energy consumption
Carbon-13 spectra are referred to the chemical during the blend preparation. Figure 3 shows that
shift of the methyl group carbons of hexamethyl
the energy consumption of the PEE/PP blend is
benzene (17.3 ppm). The 13C-NMR were carried
lower in comparison with the EPDM/PP blend,
out in the crosspolarization mode with magic- which is an advantage in terms of processability
angle spinning (CP/MAS) and CP/MAS with vari-
for the PEE/PP blend. This behavior is confirmed
able contact time. A range of contact time was by the MFI analysis.
stablished as 200 ms to 8000 ms.
MFI Analysis
RESULTS AND DISCUSSION MFI is a measure of the fluidity of the molten
polymers.12 Table II shows that the PEE/PP blend
Rheological Behavior presents a higher melt flow index (higher flow
rate in the molten state). An increase of MFI,
Torque Versus Time Analysis
which means a reduction of viscosity, indicates a
According to previous studies, it is possible to cor- more significant improvement on the flow proper-
relate torque data to viscosity of non-Newtonian ties compared with the EPDM/PP blends.
materials.11
Figures 1 and 2 show the rheological behavior
Differential Scanning Calorimetry (DSC)
of the virgin polymers (PP, EPDM, and PEE) and
blends (PEE/PP and EPDM/PP), respectively, on The mechanical properties of PP are determined
the basis of recorded torque versus time. The by its crystalline structure. Any changes in that
torque value in the plateau region, termed ‘‘stable structure will result in a change of properties, so
Table V Proton Spin-Lattice Relaxation in the Rotating Frame of PP, EPDM, PEE, and PP Blends
TH
1r (ms)
Chemical Shift d
(ppm) PP EPDM PEE PEE/PP EPDM/PP
13
Figure 6 C-NMR/CP/MAS spectra of (a) PP, (b) PPE, and (c) EPDM.
it is essential to determine the effect of elas- tion on the crystallization of polypropylene is com-
tomer blending on the crystalline structure as plicated because of the sensitivity of the PP mor-
well as on the melting and crystallization behav- phology to the temperature of crystallization. The
ior of PP.12 – 14 conventional and most widely occurring crystal
The evaluation of the effect of elastomer addi- structure of PP is a monoclinic, denominated a
13
Figure 7 C-NMR/CP/MAS spectra of (a) the PPE/PP blend and (b) the EPDM/
PP blend.
form. It is also observed that occasionally PP can evaluated by the ratio between the enthalpy of
crystallize in a hexagonal or b form.12 fusion of the blend and the enthalpy of fusion of
The primary variable affecting crystallinity in the perfectly crystalline PP ( DHPP Å 209 J/g).
PEE and EPDM is the organization of ethylene Table III shows the degree of crystallinity in
sequences and can be represented by an ortho- weight percent of PP and PP blends.
rhombic unit cell as for polyethylene.15 As should be expected, the results show that
DSC cooling and heating curves illustrating the blends present lower crystallinity degrees in
melting and recrystallization behavior of the pure relation to pure PP. In the composition analyzed,
polymers and PP blends are shown in Figures 4 it a difference was not observed between the PEE/
and 5, respectively. Both blends show broad melt- PP and EPDM/PP blend crystallinity.
ing behavior, which is probably related to changes Figure 5 shows that there is practically no
on the distribution of PP crystal morphology when change in the crystallization behavior of the PP
elastomers are added. The melt temperatures of matrix when different elastomers were added.
pure PP, PEE/PP, and EPDM/PP blends occur at The PEE/PP curve shows a peak that appears at
about 1607C, as shown in Figure 4. No melting about 407C, indicating the presence of the crystal-
peak was detected in the EPDM curve, character- line portion of PEE.
izing its amorphous nature. However, a deflection In terms of miscibility, blends are described as
can be observed in the PEE melting curve at about miscible, semimiscible, or immiscible. Generally
607C, indicating a certain degree of crystallinity. speaking, miscible mixtures present strong inter-
The degree of crystallinity of the PP blends was action between polymers; just one phase and a
PP 555 { 5 35 { 5 5{1 25 { 5 35 { 5
PEE/PP 340 { 35 15 { 1 60 { 1 50 { 5 130 { 10
EPDM/PP 320 { 40 15 { 1 65 { 5 60 { 5 140 { 10
single sharp glass transition ( Tg ) are identified. Table V exhibits the values of T H 1r of the virgin
For semimiscible blends, two values of Tg are de- polymers and the PEE/PP and EPDM/PP blends.
tected. Immiscible blends are biphase systems in Analyzing the value of T H
1r , it can be concluded
which the continuous phase is formed by the poly- that the elastomers addition does not affect the
mer that is present in higher quantity. These sys- values of T H
1r of the PP. This behavior indicates
tems present two values of Tg that are similar to that the polymers are immiscible and a phase sep-
those of the two homopolymers. aration has occurred. These results are in accor-
Analyzing the DSC results listed in Table IV, dance with DSC analysis.
it can be concluded that in the EPDM/PP blend, Figures 6 and 7 show the 13C-NMR spectra ob-
PP glass transition temperature was displaced to tained by CP/MAS technique for the virgin poly-
lower temperatures (from 042 to 0477C). This mers and PP blends, respectively.
behavior can be explained by the fact the inclu-
sions of the elastomer present a higher thermal
expansion coefficient in relation to the PP matrix. Mechanical Properties
The cooling of the blend results in a negative hy-
drostatic pressure that acts on the elastomeric Tensile Strength
particles, and thus thermal tensions that are gen-
erated can be responsible for the decrease of the Three elements dictate the mechanical properties
EPDM glass transition temperature. The same of polymer blends: crystallinity, morphology, and
behavior can be observed for the PEE/PP blend. the interfacial properties. The first one can be es-
The PEE glass transition temperature was dis- timated from the DSC experiments, the second
placed from 047 to 0547C. The results of DSC one from detailed morphological studies, and the
analysis indicate that the EPDM/PP and PEE/ last one may be deduced from the mathematical
PP blends are immiscible on the composition ana- models.
lyzed. Table VI shows that PEE/PP and EPDM/PP
blends present similar tensile properties—stress
at break ( sb ); Young’s modulus (E); and tough-
ness. These results indicate that no significant
Proton Spin-Lattice Relaxation Time
changes in tensile properties can be related to the
It is possible to detect, by high resolution, solid- similar crystallization behavior of the blends. As
state, pulsed Fourier-transformed (FT) 13C-NMR expected, the addition of elastomers to PP matrix
spectroscopy, the heterogeneous domains in poly- resulted in a decrease of stress at the break and
mer blends and estimate their size because of the Young’s modulus, and an increase of toughness.
existence of a substantial relaxation time differ- These data can be viewed as the result of the low-
ence in the specific carbon between distinguish- ering on the crystallinity of the blends in relation
able regions.16 to pure PP.
The measurements of proton spin-lattice relax-
ation time in the rotating frame ( T H1r ) make possi- Impact Strength
ble the evaluation of blend behavior in terms of
sample homogeneity, and consequently give some The impact test is commonly accepted as a mea-
indication of blend miscibility.17,18 sure of the toughness of a material. The results
CONCLUSION