Chinese Journal of Chemistry, 2005, 23, 665—668 Communication

Effect of Comonomer Ethylene on Plateau Modulus of Crystal-

line Ethylene-propylene Random Copolymer with Broad
Molecular Weight Distribution

DING, Jian(丁健) XU, Ri-Wei(徐日炜) DING, Xue-Jia(丁雪佳)

YU, Ding-Sheng*(余鼎声)
College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Ethylene-propylene random copolymer with ultra-high molecular weight (UHPPR) and broad molecular weight
distribution (MWD) was prepared with Ziegler-Natta catalyst. The viscoelastic behavior of UHPPR has been inves-
tigated by means of oscillatory rheometer at 180, 200 and 220 ℃. The loss modulus (G″) curves of 180 and 200 ℃
present a pronounced maximum at 38.10 and 84.70 r/s, respectively. For the first time, this makes it possible to di-
0
rectly determine the plateau modulus ( GN ) of crystalline ethylene-propylene random copolymer with broad MWD
in a certain experimental temperature G″(ω) curve. The plateau modulus of UHPPR is 4.51×105 and 3.67×105 Pa
at 180 and 200 ℃ respectively, increasing with random incorporation of comonomer ethylene into the molecular
chains and being independent of molecular weight.

Keywords ethylene-propylene random copolymer, broad molecular weight distribution, plateau modulus, co-
monomer

Introduction content have been reported,1,3,7 but ethylene-propylene

The plateau modulus GN0 is an important material
parameter and is associated with the molecular archi-
tecture of the polymer. The plateau modulus can be ob-
tained via the following equation: 1
2 a
π ∫−∞
GN0 ＝ G ''dln ω
where ω is angular frequency, and a is the upper limit
before the transition zone is entered. As long as G″(ω)
curve shows a well pronounced maximum in a linear
natural logarithm plot to be followed by a decrease and
an onset of the main transition, it is reasonable to ex-
trapolate to high or low frequency and to calculate the
plateau modulus via Eq. (1). Both high molecular
weight and narrow MWD facilitate this integration
method. Therefore, the values of the plateau modulus of
atactic, isotactic polypropylene (a-PP, i-PP) and amor-
phous ethylene-propylene copolymer with monodis-
perse, which were produced with metallocene catalyst,
have been determined from Eq. (1).2-7
Due to the broad MWD, conventional molecular
weight and the small window of rheological measure-
ments for crystalline ethylene-propylene random co-
polymer (PPR) prepared with Ziegler-Natta catalyst, it
is usually impossible to determine the plateau modulus
by integration method. In fact, the GN0 values for rub-
bery ethylene-propylene copolymer with high ethylene
random copolymer with low ethylene content has not
been reported until now. In order to determine the pla-
teau modulus of Ziegler-Natta catalyzed ethylene-pro-
pylene random copolymer, its molecular weight must be
high. This paper reported determination of the plateau
modulus of UHPPR by means of integration of G″(ω)
(1) curves at 180 and 200 ℃, respectively. Further, co-
monomer ethylene and molecular weight effect on the
plateau modulus were also discussed.
Experimental
Characterizing the materials
The UHPPR and PPR samples used in this study
were kindly provided by Yangzi Petrochemical Com-
pany Ltd. The molecular characteristics of the material,
weight average molecular weight (Mw), number average
molecular weight (Mn) and molecular weight distribu-
tion MWD (Mw/Mn) were determined by size exclusion
chromatography, using 1,2,4-trichlorobenzene (TCB) as
solvent at 140 ℃. DSC measurements were carried out
on a Perkin-Elmer Pyris-1 series differential scanning
calorimeter under a flowing nitrogen atmosphere. The
melting point Tm was measured using the second heat-
ing curves of 6 mg samples (heating rate 10 ℃/min).
The ethylene content data of UHPPR and PPR were
determined by FTIR (Table 1).

* E-mail: yuds@mail.buct.edu.cn; Tel.: 86-10-64434849; Fax: 86-10-64433718

Received November 16, 2004; revised February 2, 2005; accepted March 15, 2005.

© 2005 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
666 Chin. J. Chem., 2005, Vol. 23, No. 6 DING et al.

Table 1 Molecular characteristics of UHPPR and PPR

Sample Mw/(g•mol－1) MWD Ethylene content/mol% Tm/℃
UHPPR 1405000 5.40 4.0 148.4
PPR 767000 6.18 6.7 143.4

Rheology
The rheological measurements were conducted with
a Rheometrics mechanical spectrometer 2ARES-9A
with a parallel plate geometry of 25 mm in diameter.
The sample was cold-compressed and then annealed for
10 min at 200 ℃ in vacuum to form a small disk of 25
mm in diameter with a thickness of about 1 mm. For
dynamic oscillatory tests, the angular frequency ω var-
ied from 0.01 to 100 r/s, and the temperature was at Figure 2 Storage modulus G′ and loss modulus G″ as a func-
180—220 ℃. Measurements were conducted under a tion of angular frequency ω at 180, 200 and 220 ℃ for PPR.
flowing nitrogen atmosphere to avoid thermo-oxidative
degradation. Table 2 Characteristics of viscoelastic properties for Ziegler-
Natta catalyzed UHPPR and PPR
Results and discussion Temp./ ωc/ G c/ τc/ ωm/ τm/
Sample
Frequency dependence of modulus ℃ (r•s－1) (Pa×104) s (r•s－1) s
Figures 1 and 2 show frequency dependence of G″ 180 0.1084 2.619 9.225 38.10 0.0262
and G′ at 180, 200 and 220 ℃ for UHPPR and PPR, UHPPR 200 0.2312 2.185 4.325 84.70 0.0118
which present the bigger viscosity at low frequencies, 220 0.3715 1.835 2.692 — —
and higher elasticity at high frequencies. G′ is more
sensitive to angular frequency than G″ in the melt. At 180 1.0865 2.937 0.920 — —
low frequencies, the G′ of UHPPR shows non-terminal PPR 200 1.7706 2.374 0.565 — —
behavior and a deviation from the slope of 2, similar to 220 2.9354 2.215 0.341 — —
that observed for PP-clay nano-composites of more than
6% clay.8 The loss modulus G″ also shows a deviation
from the slope of 1. The reason may be that the longer ωc ∝ (1/ η0 )a ' and Gc ∝ ( M n / M w )b (2)
molecular chains in the sample are not fully relaxed.
where both a′ and b are constant parameters, and η0 is
zero shear rate viscosity. The values of ωc and Gc are
presented in Table 2. Taking into account ultra-high
molecular weight for UHPPR, the ωc is far smaller, and
the Gc is as much as that of PPR and i-PP with conven-
tional molecular weight and broad MWD.9-11
Identification of the G″(ω) peak
Figure 3 shows dlog G″/dlog ω plots against log ω
for UHPPR at 180, 200 and 220 ℃. As seen in Figure 3,
it is apparent that dlog G″/dlog ω equals zero for two
curves of UHPPR at 38.10 and 84.70 r/s at 180 and 200
℃ respectively, where it represents the position of G″
peaks. It is well known that the reliability of oscillation
measurement at ω＞100 r/s is highly questionable due
Figure 1 Storage modulus G′ and loss modulus G″ as a func- to apparatus limitations. Thus, the frequency of 38.10
tion of angular frequency ω at 180, 200 and 220 ℃ for UHPPR. and 84.70 r/s at G″ maximum is far less than 100 r/s at
180 and 200 ℃, respectively.
As shown in Figures 1 and 2, both G′ and G″ are In order to test the molecular weight dependence of
equal at one point where angular frequency and the G″(ω) maximum, the dlog G″/dlog ω plots against
modulus are called ωc and Gc, which are related to Mw log ω are also given in Figure 3 for PPR at 180 and 200
and MWD respectively. In particular, it was found for ℃. Compared with UHPPR, there is no point where
PP that:9

© 2005 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Ethylene-propylene random copolymer
Figure 3 dlog G″/dlog ω as a function of log ω for both
UHPPR at 180, 200 and 220 ℃, and PPR at 180 and 200 ℃.
dlog G″/dlog ω equals zero for PPR in Figure 3. This-
suggests that high molecular weight be responsible for
the pronounced maximum in the G″(ω) curve in the
UHPPR.
Additionally, the viscoelastic behavior of Ziegler-
Natta catalyzed PP homopolymer with the Mw and
MWD similar to that of UHPPR was also characterized
by small amplitude oscillatory measurement at 180 and
200 ℃. G″ peaks of 180 and 200 ℃ were located at
34.35 and 69.21 r/s, respectively. These results further
illustrate that the well pronounced peaks of G″(ω)
curves in Figure 1 were ascribed to ultra-high molecular
weight fractions in the UHPPR. The related data will be
reported in another paper.12
Furthermore, the relaxation time τm and τc are de-
fined as the inverse of ωc and angular frequencies ω (ωm)
where G″ reaches maximum, and can be calculated by
the following equation:13,14
τm＝1/ωdG˝/dω＝0 (3)
The τm values listed in Table 2 were decreased with
increasing temperature. The experimental results by
Raju et al.14 showed that ωm was increased with de-
crease of molecular weight for linear polybutadiene,
demonstrating that τm was decreased from Eq. (3) as
molecular weight was decreased. Therefore, the ωm of
PPR, if observed, would be larger than that of UHPPR
and 100 r/s, leading to that it is reasonable not to ob-
serve the ωm of PPR in Figure 3.
Comonomer ethylene effect on the plateau modulus
GN0
As discussed above, it is obvious that the G″ curve
has a pronounced maximum for UHPPR at 180 and 200
℃ respectively. Miyata et al.7,15 reported that the G″
versus ln ω curve was numerically integrated from
ln ω＝－∞ to the maximum of G″, and the result was
doubled to obtain the GN0 value. Moreover, the G″
versus ln ω curve shows symmetry at 180 ℃ for
UHPPR (Figure 4). Therefore, for the first time, it was
able to extrapolate G″ to zero for low angular frequen-
© 2005 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem., 2005 Vol. 23 No. 6 667
cies ω in a natural logarithm plot (Figure 4) at different
temperatures for Ziegler-Natta catalyzed UHPPR.
Figure 4 Loss modulus G″ versus angular frequency ω in a
linear natural logarithm plot for UHPPR at 180 and 200 ℃.
According to Eq. (1), the values of GN0 were found
to be 4.51×105 and 3.67×105 Pa at 180 and 200 ℃,
respectively. The value of GN0 at 180 ℃ is slightly
higher than the GN0 of 4.27×105 Pa reported for met-
allocene catalyzed i-PP with conventional molecular
weight and MWD of 2.4 at 190 ℃ and the GN0 of
4.28×105 Pa for i-PP with the similarity to molecular
weight of UHPPR,2,12 and lower than GN0 of 1.06×106
Pa for rubbery ethylene-propylene copolymer contain-
ing the ethylene content of 62.8 mol%.15 These results
indicate that the incorporation of ethylene into i-PP
chains increased the value of GN0 for crystalline ethyl-
ene-propylene random copolymer, also demonstrating
that GN0 is independent of molecular weight.
The entanglement density νe can be expressed as
follows:
ρ GN0
ν e＝ ＝ (4)
Me RT
The νe values of UHPPR at 180 and 200 ℃ are
higher than those of i-PP with broad MWD, respec-
tively.12 These indicate that entanglement density νe has
been increased due to randomly introducing ethylene
into PP main chains for UHPPR. On the other hand, νe
has been decreased with increase of temperature.
Conclusion
For Ziegler-Natta catalyzed ethylene-propylene ran-
dom copolymer with ultra-high molecular weight and
broad MWD, the G″(ω) curves of 180 and 200 ℃ for
UHPPR show a maximum at 38.10 and 84.70 r/s, re-
spectively, where dlog G″/dlog ω equals zero. Therefore,
it is the first time to determine its plateau modulus GN0
value by integration method according to G″(ω) curves
at 180 and 200 ℃ for ethylene-propylene random co-
polymer with low ethylene content and broad MWD.
668 Chin. J. Chem., 2005, Vol. 23, No. 6 DING et al.

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(E0411166 LI, L. T.; LING, J.)

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