SCIENCE CHINA

Chemistry
• FEATURE ARTICLES • May 2012 Vol.55 No.5: 698–712
· SPECIAL ISSUE · In Honor of the 80th Birthday of Professor WANG Fosong doi: 10.1007/s11426-012-4531-z

Microstructure, morphology, crystallization and rheological

behavior of impact polypropylene copolymer
SHANG-GUAN YongGang, CHEN Feng & ZHENG Qiang*
Key Laboratory of Macromolecular Synthesis and Functionalization, Ministry of Education; Department of Polymer Science and Engineering,
Zhejiang University, Hangzhou 310027, China

Received December 9, 2011; accepted December 27, 2011; published online March 28, 2012

Impact polypropylene copolymer (IPC), named polypropylene catalloy, not only possesses excellent impact property, but also
presents good rigidity. Its superior performances result from the complicated composition and microstructure. In the present
article, recent progress in the studies on microstructure, morphology, crystallization and rheological behavior of IPC is sum-
marized, and findings of the authors and their collaborators are reported. In general, IPC is divided into three components, i.e.,
ethylene-propylene random copolymer (EPR), a series of different segment lengths ethylene-propylene copolymer (EbP) and
propylene homopolymer. The reasonable macromolecular structures of EbP and a multilayered core-shell model of dispersed
phase structure in IPC were proposed, in which the dispersed phase consists of an outer EbP shell, an inner EPR layer and an
EbP core. It is found that the annealing at melt-state may lead to an abnormal phase inversion, and the phase inversion disap-
pears when temperature cools down to room temperature. The cause of phase inversion is ascribed to the existence of EbP
component, which results in the stronger activity of the dispersed phase. The crystalline structure and morphologic results con-
firm the formation of -iPP in IPC. Furthermore, it is found that the ethylene content in IPC and cooling rate of the samples
have an important influence on the formation of -iPP. Based on the crystallization kinetics analyzed by Lauritzen-Hoffman
theory, crystallization behavior of different IPC samples is discussed and it is proposed that the dilution effect of ethylene-
propylene copolymer has a more remarkable influence on surface nucleation than on crystal growth. In addition, annealing at
high temperature can result in the changes of chain structure for IPC, and this instability is ascribed to the oxidative degrada-
tion and crosslink reaction mainly in iPP component.

microstructure, morphology, crystallization behavior, rheological property, impact polypropylene copolymer

1 Introduction propylene random rubber (EPR) and ethylene-propylene-

diene monomer (EPDM), have been developed in the past
Due to its poor impact property, isotactic polypropylene two decades and among which iPP/EPR blend is one of the
(iPP), as an important thermoplastic, is limited in many ap- most important modified iPP products.
plications, especially at low temperature. A great deal of Although iPP/EPR blends can be prepared through melt
effort has been made to improve the impact property of iPP mixing, it has been documented that iPP/EPR blends are
immiscible in melt-state and phase-separation may take
through physical or chemical methods. It is generally be-
place [68]. Since phase-separation can lead to a coarse
lieved that adding a variety of elastomers [15] into iPP is
phase structure and consequently a low interfacial adhesion,
one of the physical methods. Subsequently, various modi-
the iPP/EPR blends prepared by physical methods exhibit
fied iPP containing different elastomers, such as ethylene-
worse strength. Recently, a novel copolymerization tech-
nology which produces an in-situ polypropylene copolymer
*Corresponding author (email: zhengqiang@zju.edu.cn) by two-step polymerization has been widely applied in in-

© Science China Press and Springer-Verlag Berlin Heidelberg 2012 chem.scichina.com www.springerlink.com
 Shang-Guan YG, et al. Sci China Chem May (2012) Vol.55 No.5 699

dustry [912], and the two-step polymerization includes tion due to its two-step continuous polymerization. Previous
homo-polymerization of propylene and subsequent copoly- work has reported that IPC mainly consists of three compo-
merization of propylene and ethylene in a gas-phase reactor sitions including EPR, EbP with different sequence lengths
by using a special ZieglereNatta catalyst [11, 12]. The and iPP [3035]. Through temperature-gradient extraction
products prepared by the continuous two-step copolymeri- fractionation (TGEF), IPC can be fractionated into several
zation are called polypropylene catalloy (PP-cat) or impact compositions depending on the extraction temperatures used.
polypropylene copolymer (IPC). It is known that IPC has a The composition of IPC has been investigated and con-
rather complex composition and microstructure, and pre- firmed by authors through differential scanning calorimetry
sents a good tensile strength and an excellent impact (DSC), wide angle X-ray diffraction (WAXD), dynamic
strength, even at low temperatures, as compared with the mechanical analysis (DMA) and fourier transform infrared
iPP/EPR or iPP/EPDM blends obtained by mechanical spectroscopy (FTIR) [1719].
mixing [12, 13]. It is suggested that the excellent properties IPC-A is extracted through TGEF by using a modified
of IPC are ascribed to its complicated composition and Kumagawa extractor. Here the IPC-A samples used are de-
phase structure since a phase-separated morphology of IPC fined as PEP20, PEP40 and PEP60, respectively, in which
is observed. Hence, it is necessary to study the composition, capital E stands for ethylene component and the numbers
microstructure and morphology of IPC. Moreover, the me- stand for its percentage used in the stage of gas-phase co-
chanical properties of IPC may be affected by the crystalli- polymerization. Figure 1(a) gives the composition data of
zation behavior of iPP component, so the crystallization IPC-A obtained through fractionation. It is clear that both
behavior is worth exploring. the contents of random copolymer and propylene homo-
The phase morphology of multi-component polymers polymer are higher than those of block copolymer for all
can be detected by phase contrast optical microscopy IPC-A samples, and the contents of block copolymer of all
(PCM), scanning electron microscopy (SEM), transmission three IPC-A are almost equal, while the random copolymer
electron microscope, etc. and also, a polarized optical mi- increases and propylene homopolymer decreases with the
croscopy (POM) or PCM equipped with a temperature con- increase of ethylene content. Figure 1(b) gives the eth-
trolled hot stage can monitor the time evolution of mor- ylene content of each component calculated from FTIR data.
phology or structure. Being quite sensitive to the change of Moreover, the ethylene contents of both random copolymer
structure or morphology, dynamic rheological testing is
considered to be a powerful tool to provide some valuable
information which is impossible or difficult to obtain from
traditional morphological observation methods. Further-
more, on account of small-strain amplitude, dynamic rheo-
logical testing can avoid the destruction of structure or
morphology [14].
As for the study on the composition and macromolecular
structure of multi-component polymers, fractionation is an
essential approach. Some previous researches on the compo-
sition of IPC [12, 15, 16] involve solvent fractionation and
thermal fractionation. In the present work, two kinds of IPC
samples are used. One is the laboratory product named
IPC-A, whose compositions vary from PEP20 to PEP60; the
other is a commercial product, SP179, purchased from Si-
nopec Qilu Petrochemical Co. of China, and named IPC-B.
n-Octane is used as a solvent to successively extract the IPC
under different temperatures through temperature-gradient
extraction fractionation. Some recent progress on the study
of IPC concerning the following four aspects is summarized,
mainly findings by the authors, including (1) the complex
composition , (2) the microstructure and morphology
[16, 17, 2024], (3) the crystallization behavior [21,2426],
and (4) the rheological properties [2729].

2 Fractionation and composition of IPC

Figure 1 Fractions distribution of IPC-A (a) and ethylene weights in the
As mentioned above, IPC shows a rather complex composi- fractions (b) [18].
700 Shang-Guan YG, et al. Sci China Chem May (2012) Vol.55 No.5

and propylene homopolymer increase regularly from PEP20

to PEP60. These results mean that the structures of both
EPR and EbP fractions change regularly and more ethylene
segments or longer ethylene segments exist in the EPR and
EbP chains with the same weight when the ethylene content
in IPC increases.
It is well-known that a single glass-transition temperature
(Tg) for binary blends is the evidence of miscibility on a
dimensional scale between 10 and 30 nm [36]. The iPP/EPR
blends have been proved to be immiscible at molten state as
well below the crystallization temperature of iPP [6, 8, 37,
38]. Due to the low EbP content, IPC-A is regarded as a
binary blend to some extent. On the other hand, it is
acknowledged that the presence of diblock copolymer could
improve the dispersion because the diblock copolymer may
act as the compatibilizer of binary blend [13, 39, 40]. As an
indication of miscibility, the value of ∆Tg is defined as the
Tg difference between EPR and iPP component in IPC-A.
Figure 2 presents the dependence of ∆Tg on the composition
of IPC-A. The value of ∆Tg decreases from PEP20 to
PEP60, indicating that the increase of ethylene content has a
positive effect on improving the miscibility of the samples.
Since it is widely accepted that the interaction between iPP
and EPR is very weak and its composition has little effect
on the miscibility [41, 42], the above results indicate that
the dependence of ∆Tg on the composition of IPC-A may
result from the occurrence of EbP component in IPC-A ra- Figure 3 DSC reversible heat flow (a) and heat flow (b) for F50 [19].
ther than from the content variations of EPR and PP.
The authors also have investigated the commercial IPC
[19] purchased from SINOPEC Qilu Petrochemical, China. iPP crystals with low lamellae thickness, indicating that the
The samples are fractionated into three fractions defined as F50 mainly contains EPR and a very small amount of PE or
F50, F100 and F125, in which the numbers stand for the ex- iPP segments which can form crystals with thin lamellae.
tracting temperature. Figure 3(a) shows the reversible heat On the other hand, only a single glass transition peak for
flow for F50. An obvious glass transition can be seen, which F100 fraction is observed in Figure 4(a), which is ascribed to
should be attributed to EPR. Nonexistence of Tg attributed the EPR component. This peak indicates that the F100 frac-
to iPP fraction reveals that the F50 mainly consists of ran- tion contains a small amount of EPR even it appears much
dom copolymer and contains few propylene homopolymer. weaker than that of F50 fraction. Since the EPR chains
Moreover, there exist two tiny peaks as seen in Figure 3(b) should be extracted at 50 °C, EPR in F100 fraction may be
and these peaks should be attributed to the melting of PE or only some segments connecting with EbP. Furthermore, the
compatibility of EbP probably results from the simultaneous
existence of iPP segment and EPR segment. Figure 4(b)
presents the melting curve of F100. Three melting peaks,
labeled as I, II and III, appear at 144, 136 and 114 °C re-
spectively, can be observed. Since the temperatures of peak
I and II are located between the Tms of high density poly-
ethylene (HDPE) and iPP, these two peaks should be at-
tributed to the melting of iPP crystals with thin lamella.
Figure 5 gives the WAXD pattern of F100. The existence of
PE and iPP crystals indicates that F100 contains different
segment lengths of PE and iPP. Hence, peak III at 114 °C
should represent the melting of PE crystals with low perfec-
tion. On the basis of the above analysis, it is suggested that
F100 contains a series of ethylene-propylene copolymers
Figure 2 Effect of IPC-A composition on the Tg difference between EPR with different segment lengths, and the reasonable macro-
and iPP component in IPC-A [18]. molecular structures of F100 are presented in Figure 6.
 Shang-Guan YG, et al. Sci China Chem May (2012) Vol.55 No.5 701

Figure 6 Schematic diagram of probable chain structure of F100 [19].

Figure 4 DSC reversible heat flow (a) and heat flow (b) for F100 [19].
Figure 7 Temperature dependence of loss tangent (tanδ) for IPC and its
fractions at a frequency of 10 Hz and a heating rate of 3 °C/min [17].

Figure 5 WAXD patterns of F100 [19].

Figure 8 Temperature dependence of loss tangent (tanδ) for IPC and
LDPE at a frequency of 10 Hz and a heating rate of 3 °C/min [17].
Figure 7 gives the temperature dependence of loss tan-
gent (tanδ) for IPC and its fractions. Three glass transitions
can be seen for IPC and EbP fraction and only a single peak served at 113.5 °C for IPC. In view of the existence of
can be observed for iPP and EPR fractions. Compared with peak at about 113 °C for both IPC and EbP fractions, it
iPP and EPR fraction, it can be inferred that the peaks at is suggested that this peak results from the glass transi-
14.5 °C and 37 °C for IPC belong to the glass transitions tion of PE segment, and the speculation above is con-
of iPP and EPR respectively. It is interesting that a peak firmed according to the DMA result of LDPE, as shown
which has never been reported in previous literature was ob- in Figure 8.
702 Shang-Guan YG, et al. Sci China Chem May (2012) Vol.55 No.5

3 Microstructure and morphology of IPC present work as well the possible structure of EbP, a modi-
fied phase model of IPC is proposed, as shown in Figure 10.
In this model, the dispersed particle has an EbP core and
As a result of complex composition of IPC, the microstruc-
two layers, and the outer layer is EbP and the inner one is
ture and morphology of IPC are also complicated. Due to
EPR. It is noted that some EbP chains may pass through the
the immiscibility of iPP/EPR blend at melt state, IPC exhib-
EPR layer and connect the core and shell as bridges. Ac-
its three glass transitions as shown in Figure 7, indicating
cording to Figure 6, the structures of EbP can occur as four
that it is in phase-separated state. In addition, since the iPP
cases marked as I, II, III and IV, respectively. The chains
component tends to crystallize below the melting point,
dominated by iPP segments are denoted as type I, and they
crystallization and phase-separation may interfere with each
are mostly located in the shell to improve the interaction
other, and subsequently a more complicated structure is
between dispersed phase and continuous phase. The chains
formed. In the past two decades, some investigations con-
dominated by PE segments are denoted as type II, and they
cerning the phase structure and crystalline structure have
tend to form the PE-rich core. The chains with equivalent
been reported [15, 17, 21, 2324, 35, 4346]. Here, some
iPP and PE segments are denoted as type III, and they may
recent progress in the microstructure and morphology of
be located in the outer shell or the inner core, and some
IPC is summarized [17, 23, 24].
even cross the EPR layer to form the EbP bridges. The last
Figure 9 gives the SEM micrographs of fracture surface
type, IV, is the chain containing some ethylene-propylene
after being etched by xylene. It can be seen that there exists
random sequences which may stay anywhere in EbP com-
a two-phase structure, and the dispersion is rather uniform.
ponents.
Figure 9(b) gives the amplified micrograph of one area in
In the case of EbP cores being completely wrapped by
Figure 9(a). The sizes of the dispersed particles are larger
EPR layers, the removing of EPR layers by xylene would
than 0.5 μm, a critical dimension [47], beyond which the
lead to the disappearance of EbP cores which have weaker
dispersed particles could promote crazing and improve the
EbP bridges connected with the outer shell, resulting in the
fracture resistance of polymeric materials. As seen from the
formation of the holes on the fracture surface indicated as
amplified micrograph, the dispersed phase presents three
‘A’. For the cores partially wrapped by EPR layers, the EPR
different cases: (i) isolated holes marked as ‘A’, (ii) holes
layers are removed by xylene, while the cores remain,
containing a smaller granule marked as ‘B’, and (iii) aggre-
forming the holes with a small granule, indicated as ‘B’.
gate granules marked as ‘C’. As previously described, the
When the dispersed particles get together and the removing
chains of EbP contain not only the crystallizable ethylene
of EPR layers is hindered due to the outer shell of EbP, the
and propylene segments, but some ethylene-propylene ran-
aggregation of dispersed particles indicated as ‘C’ can be
dom sequences. The reasonable macromolecular structures
observed on the fracture surface. Figure 11 shows the trans-
of EbP are presented in Figure 6. On the basis of the previ-
mission electron microscope (TEM) image of IPC solution-
ous works [16, 21] and the morphologic results observed in
casting film after being annealed at 200 °C for 10 min. A
core-shell structure of dispersed phase can be seen, which
accords with the phase structure examined by AFM [21]. It is
suggested that the core-shell structure of dispersed phase is a
thermodynamic stable structure, which can be rebuilt even
after it is completely destroyed by dissolving in xylene.
Figure 12 presents the PCM images of IPC during an-
nealing at 200 °C. As phase-separation is ongoing, the

Figure 9 SEM micrographs of fracture surface of the IPC in different

magnifications [17]. Figure 10 Illustration of phase structure for IPC [17].
 Shang-Guan YG, et al. Sci China Chem May (2012) Vol.55 No.5 703

‘sea-island’ structure forms from the co-continuous struc-

ture during phase-separation, the major component forms
the continuous phase and the minor component forms the
dispersed phase usually. It is interesting that the area of
dispersed phase is much larger than that of continuous
phase in Figure 12(f). This phenomenon indicates that a
phase inversion happens in IPC during annealing, which is
usually ascribed to the lower viscosity of the minor compo-
nent in some works [48]. However, the viscosity of EPR
component is much higher than that of iPP, meaning that
Figure 11 TEM micrograph of IPC solution-casting film [17].
the cause of phase inversion couldn’t be ascribed to the dif-
ference of viscosity between iPP and EPR components.
micro-domains become larger with the increase of annealing Considering the existence of EbP, the activity of the dis-
time. Figure 12(d) shows the PCM image of IPC annealing persed phase in IPC is much stronger than that of iPP/EPR
at 200 °C for 90 min, and an obvious co-continuous struc- blend, and it makes the phase inversion possible. Due to the
ture can be observed. Subsequently, the morphology high viscosity, once the EPR forms the continuous phase, it
changes into a clear ‘sea-island’ structure with the extension is hard to be destroyed. However, when the temperature is
of annealing time. Concerning the fact that a co-continuous cooled down to room temperature, the abnormal phase
structure is one of the most important characteristics of spi- morphology disappears. As a result, the major component,
nodal demixing (SD), the phase-separation of IPC follows iPP, forms the continuous phase and the minor component,
an SD mechanism. When the annealing time increases, the EPR, forms the dispersed phase, as shown in Figure 13.
morphology hardly changes, indicating that an equilibrium Figure 14 gives the schematic diagram of the phase mor-
structure has been reached. It is worth noticing that when a phology evolution of IPC. It is believed that the disappear-

Figure 12 Phase contrast micrographs of IPC samples annealed at 200 °C for different time periods. (a) 10 min, (b) 30 min, (c) 60 min, (d) 90 min,
(e) 120 min and (f) 200 min.

Figure 13 SEM images and partial enlargement of the extracted cross- section surface of IPC after being annealed at 200 °C for 200 min.
704 Shang-Guan YG, et al. Sci China Chem May (2012) Vol.55 No.5

Figure 14 Schematic of phase morphology evolution of IPC annealed for 200 min at 200 °C during cooling: (a) in the melt state; (b) at solidification [24].

ance of the phase inversion can be ascribed to the large ten- melting point of about 150 °C demonstrated by melting test
sion induced by solidification at the phase interface and the (Figure 16), while others melt at about 160 °C. Based on the
great content difference between components. characteristics of β-iPP, it is suggested that some β-iPP
Figure 15 depicts the crystalline morphologies of iPP and crystals are formed in the crystalline phase.
IPC-A at cooling rate of 2 °C/min. For all samples, the Figure 17 gives the WAXD patterns of iPP and IPC-A
crystalline structures from melt crystallization are spheru- crystallized at the cooling rate of 2 °C/min. All of the most
lites. The contours of the crystals become more blurred with intense WAXD reflections are attributed to the lattice planes
the increase of ethylene content. It can be observed that the of α-monoclinic structures, revealing that the iPP crystals
number of spherulite and their dimension strongly depend grow dominatingly in their monoclinic α-modification. For
on composition. From iPP to PEP60, more spherulites are PEP50 and PEP60, there exists an extra reflection corre-
formed and the spherulitic structure becomes more deficient sponding to the (200) lattice planes of PE crystals, indicat-
due to the formation and quick impingement of small ing that the ethylene segment in PEP50 and PEP60 is long
spherulites. These results clearly illustrate the fact that the enough to crystallize independently. It should be pointed
content of ethylene has an influence on the crystallization out that another peak appearing at 2θ of 16.0 °C, which is
morphologies of iPP. In addition, a few micro domains as the distinct diffraction of the (300) lattice plane of β-iPP,
indicated by the white arrows are observed in the optical proves the existence of β-iPP in IPC-A. On the other hand,
micrographs of PEP50 and PEP60, which exhibit very in accords with the results obtained by optical microscopy,
strong negative birefringence. These domains possess a it can be seen that the content of β-iPP crystals increases

Figure 15 Optical micrographs of iPP and IPC-A crystallized at cooling rate of 2 °C/min. The white arrows in the pictures indicate the β-iPP (crossed
polars) [23].
 Shang-Guan YG, et al. Sci China Chem May (2012) Vol.55 No.5 705

Figure 16 Optical micrographs of the β-iPP spherulite in PEP50 speci-

mens taken during heating from the room temperature to melting tempera-
ture at (a) 145 °C and (b) 155 °C (heating rate: 10 °C/min). The white
arrows in the pictures indicate the β-iPP (crossed polars) [23].

Figure 17 WAXD patterns of iPP and IPC-A crystallized at cooling rate

of 2 °C/min [23].

with the increase of ethylene content.

4 Crystallization and melting behavior of IPC

As mentioned above, IPC samples present different micro-

structures and morphologies due to the interaction between
phase-separation and crystallization behavior, so it is nec-
essary to investigate the crystallization and melting behav-
ior of IPC experimentally and theoretically [26]. Figure 18 DSC melting traces of iPP and various IPC-A samples iso-
Figure 18 depicts the DSC melting traces of iPP and thermally crystallized at different temperatures: (a) iPP, (b) PEP20, (c)
various IPC-A samples isothermally crystallized under dif- PEP40 and (d) PEP60 [26].
ferent temperatures. It is obvious that iPP sample only pre-
sents a single melting peak at about 165 °C which can be attributed to the melting of α-iPP. The same phenomena are
706 Shang-Guan YG, et al. Sci China Chem May (2012) Vol.55 No.5

observed for PEP20. As for PEP30, PEP40 and PEP50, two compositions, even obviously lower than that of iPP, which
melting peaks can be found according to WAXD and POM coincides with other reports [50, 51]. According to the pre-
results, one of which stands for the melting of α-iPP, and vious results and analyses, it is suggested that melting point
the other, the melting of β-iPP. A small peak at about depression of IPC-A lies in two factors: the lower molecular
118 °C is ascribed to the melting of polyethylene crystal for weight of propylene homopolymer and the stronger interac-
PEP60. tion between compositions in IPC-A [46, 52].
The β-iPP content in crystalline phase of various IPC-A Figure 20 gives the spherulite growth rates measured
samples crystallized at different isothermal conditions can under isothermal and nonisothermal conditions for iPP and
be calculated from DSC data. It is found that the β-iPP con- IPC-A, respectively. It can be seen that spherulite growth
tent is dependent on both the crystallization temperature and rates of all IPC-A are smaller than those of iPP, and de-
the ethylene content. 124 °C is the most suitable tempera- crease with the increase of ethylene content. Moreover, the
ture for formation of β-iPP, and the β-iPP content is no differences in spherulite growth rates between IPC-A and
more than 7%. Due to the little content of β-iPP, the melting iPP are remarkable in low temperatures, and small in high
behavior of the β-iPP is ignored when the equilibrium melt- temperatures, which can be attributed to the low degree of
ing temperature of IPC-A is discussed. super-cooling resulting from high temperature which slows
Figure 19 gives the equilibrium melting temperatures of down the spherulite growth rate. In fact, obvious compo-
iPP and IPC-A by Hoffman-Weeks equation [49]. The nent-dependent spherulite growth rate for IPC-A from the
melting temperatures increase with the increase of crystal- amplified figure can be seen in high temperatures. Since the
lization temperature for both iPP and IPC-A, indicating viscosities of IPC-A increase with the increase of ethylene
improvement of the crystalline perfection with the increase content, these phenomena can be ascribed to the weak
of crystallization temperature. The Tom values of 187 °C for motion ability of the crystallizable propylene segments
iPP and 182 °C for IPC-A from Figure 19(b) could be ob- resulting from high viscosities. Furthermore, the spherulite
tained by extrapolating the experimental data to Tm = Tc line.
It is interesting that the Tom of IPC-A is independent of the

Figure 20 Spherulite growth rates measured at isothermal conditions (a)

Figure 19 Melting temperatures of iPP and IPC-A crystallized in differ- and nonisothermal conditions (b) for iPP and IPC-A crystallized at differ-
ent temperatures (a) and Hoffman-Weeks plots of iPP and IPC-A (b) [26]. ent temperatures [26].
 Shang-Guan YG, et al. Sci China Chem May (2012) Vol.55 No.5 707

growth rates obtained under nonisothermal conditions pre- PEP60. These kinetic differences of IPC-A impossibly result
sent similar temperature and composition dependence. from the molecular weights and polydispersity of propylene
Lauritzen-Hoffman theory [53] has been widely adopted homopolymer due to little difference for various IPC-A.
to investigate the crystallization kinetics of polymeric mate- Based on the fact that the values of Kg and σe increase with
rials. The crystallization of iPP and IPC-A can be analyzed the increase of ethylene content in the same regime [26], it
by using Lauritzen-Hoffman model. In general, the crystal can be conclude that both surface nucleation rate and crystal
phase of iPP is mainly -crystal and the crystal growth is in growth rate slow down [53, 56, 57]. Hence, a large degree of
favor along (110) lattice plane during melt-crystallization. super-cooling is required for the crystallization of IPC-A
However, on the basis of above analysis on crystalline phase with high ethylene content to enter into regime II. During
structure, it is understood that the crystal growth of PP-cats crystallization of propylene homopolymer, ethylene-
is in favor along (040) lattice plane. Until now, most of the propylene copolymer is forced to get together in the vicinity
kinetic studies on iPP crystallization proceed with the pa- of crystal growth plane. Furthermore, the mobility of eth-
rameters of (110) lattice plane. However, for those on the ylene-propylene copolymer in the vicinity of crystal growth
PP-cats, it should be more logical to calculate the fold sur- plane is very weak due to its high viscosity, which could be
face free energy, σe, by using the parameters of (040) lattice regarded as a dilution effect to hinder surface nucleation and
plane. Figure 21 gives the kinetic analysis results of noniso- crystal growth of iPP. Concerning the decrease of transition
thermal and isothermal growth data using Lauritzen- temperature of regime II to III, it is believed that the dilution
Hoffman model for iPP and IPC-A, and for iPP sample, two effect has a stronger obstruction effect on surface nucleation
lines and a transition at 138 oC could be observed. In view of than on crystal growth. In conclusion, the shifting of the
the fact that the value of nucleation parameter, Kg, in regime transition temperature of regime II to III mainly results from
II is lower than those in regime I and III, and the tempera- the dilution effect of ethylene-propylene copolymer.
tures corresponding to regime II are higher than those of
regime III, iPP sample presents a transition of regime II to III
in Figure 21, which is in accordance with other reports on 5 Rheological properties of IPC
crystallization kinetics of iPP [54, 55]. For PEP20 and
PEP40, similar phenomena can be observed though the Figure 22 gives the frequency (ω) dependence of loss tan-
transition temperature decreases with the increase of eth- gent (tanδ) for IPC and its fractions. It can be observed that
ylene content, and no transition could be observed for there is a peak in low ω for IPC and EbP. However, no peak

Figure 21 Kinetic analysis of nonisothermal and isothermal growth data of iPP and IPC-A under U* = 6270 J/mol and T∞ = Tg – 30 K [26].
708 Shang-Guan YG, et al. Sci China Chem May (2012) Vol.55 No.5

indicates that the dynamic viscoelastic function deviates

from the classical linear viscoelastic theory. The value of G'
of blend II is higher than that of IPC while blend I has a
lower G' value compared with IPC, indicating that the de-
gree of heterogeneity in blend II is higher than that in blend
I. On the other hand, the loss tangent (tanδ) peak for blend
II is located at a higher frequency as compared with IPC,
though that of blend I is lower. These facts further indicate
that the performance of long relaxation unit in blend II is
more significant than those of others. Due to the high vis-
cosity of EPR, it is suggested that the network structure of
the dispersed phase becomes more perfect which leads to
more notable ‘second plateau’.
Figure 22 Frequency (ω) dependence of loss tangent (tanδ) for IPC and It is known that polymer processing in general leads to
its fractions at 170 °C [29]. the changes in chemical structure of polymer and affects the
ultimate properties of material. Due to the considerable sig-
nificance of optimizing the properties of polymer materials,
much attention has been paid to the thermal and
thermo-oxidative degradation of polymer chains [27,
5860]. The possible change in chemical structure of IPC
during melt-state annealing is investigated by using rheo-
logical measurements. Figure 24 presents isothermal fre-
quency dependence of G′ for pure IPC in different tempera-
tures under atmosphere of air and N2, respectively. It can be
observed that G′ drops with the decrease of ω at 190 °C in
air. At 210 °C, G′ obviously increases in low ω region, and

Figure 23 Frequency (ω) dependence of (a) dynamic storage modulus

(G'), (b) tan δ for IPC and iPP/EPR blends at 170 °C [29].

appears for EPR and iPP fraction. Since IPC and EbP are
both multi-component polymers, this phenomenon indicates
the existence of long relaxation unit in IPC and EbP. Figure
23 shows the frequency dependence of dynamic storage
modulus (G') and loss tangent (tanδ) for IPC and two
iPP/EPR blends. The proportion of iPP/EPR in blend I is
78.5/21.5 by weight, which is consistent with that of IPC.
The proportion of iPP/EPR in blend II is 70/30, which ac-
cords with the proportion of iPP/(EPR+EbP) of IPC. Obvi- Figure 24 Relationship between G′ and ω for pure IPC at different tem-
ously, in both blends the ‘second plateau’ appears, which peratures under air (a) and under N2 (b) [28].
 Shang-Guan YG, et al. Sci China Chem May (2012) Vol.55 No.5 709

‘second plateau’ appears. At 230 °C, the ‘second plateau’

appears earlier and higher than that at 210 °C. It is widely
accepted that the appearance of ‘second plateau’ usually
indicates the formation of high-order structure such as
sol-gel transition, crosslinking and phase-separation etc in
multi-component system [61]. It should be noted that in N2,
‘second plateau’ could hardly be observed at low ω for pure
IPC and its G′-ω curve is similar to that of iPP, no matter at
170 °C or 230 °C. These results indicate that the appearance
of ‘second plateau’ has nothing to do with phase-separation
but should be attributed to the change of chain structure in
high temperatures.
Figure 25 presents the dependences of G′ and dynamic
loss modulus (G′′) on time at 230 °C in air. A notable raise
of G′ can be observed after the standstill stage in the first 10
min, while the G′′ seems unchanged at the early stage and
then slightly increases. It should be pointed out that at the
early stage, the value of G′′ is higher than that of G′, and
they match together at 73 min owing to the faster growth
rate of G′. These phenomena are often observed in sol-gel
transition, cure or crosslinking of polymer materials
[6263], indicating that some changes in chain structure
take place in IPC melt, and G′ may effectively reflect the
instability of IPC melt. Figure 26 shows the evolutions of
rheological functions in different temperatures for pure IPC
and IPC1 in air. Here, the number following IPC stands for
the weight percentage of antioxidant. For pure IPC, there
exists a small drop for G′, followed by a slight raise at
190 °C. With the increase of temperature, the drop period
becomes shorter, while the following increase of G′ be- Figure 26 Time dependence of G′ for pure IPC (a) and IPC1 (b) at
different temperatures [28].
comes more apparent. Moreover, at 230 °C, the value of G′
even rapidly increases following a transient and very slight
drop. The drop of G′ under isothermal condition probably needed gets shorter with the increase of temperature. Taking
results from the stress relaxation or degradation of polymer these facts into consideration, the drop of G′ can’t be as-
chain. To illustrate the reason for decrease of G′, we have cribed to the relaxation of IPC melt, but may be attributed to
conducted the relaxation experiments for pure IPC at the degradation of polymer chain. Due to the crosslink ten-
190 °C. However, the results show that the relaxation time dency of EPR and iPP in high temperature, the increase of
of pure IPC at 190 °C only takes no more than 100 s [27]. G′ may result from the crosslink reaction in IPC melt. It is
The IPC melt possesses a faster relaxation rate and the time found that after the samples subjected to dynamic time
sweep experiment at 210 and 230 °C were extracted in
boiling xylene for 48 h, some undissolved yellow and black
substances remained, indicating that the crosslink reaction
indeed occurs in pure IPC under high temperatures and the
remaining substances are the products from rheological ex-
periment under high temperatures. These facts prove the
above deduction that the raise of G′ results from the cross-
linking in pure IPC.
As for the mechanism of crosslinking for EPR and iPP,
some works have been reported [64, 65]. As far as iPP is
concerned, the crosslinking includes two steps: oxidative
degradation and recombination of the degraded products;
and for EPR, the crosslinking can occur by two ways: addi-
tional crosslinking agent or the free radical produced from
Figure 25 Time dependence of G′ and G′′ for pure IPC samples at its thermal degradation. Figure 26(b) shows time depend-
230 °C [28]. ence of G′ for IPC1 under different temperatures. Compared
710 Shang-Guan YG, et al. Sci China Chem May (2012) Vol.55 No.5

temperatures for PEP60. The dilution effect of ethylene-

propylene copolymer has a more obvious influence on sur-
face nucleation than on crystal growth. When reaching cer-
tain degree, the phase-separation between iPP and EPR
fractions leads to the existence of ‘second plateau’. Moreo-
ver, the annealing at high temperature results in the changes
of chain structure of IPC. The instability of IPC melt is as-
cribed to the occurrence of oxidative degradation and cross-
linking mainly in iPP component.

This work was supported by the National Basic Research Program of Chi-
na (2005CB623800), National Natural Science Foundation of China
Figure 27 Time dependence of G′ for IPC at 230 °C in air and in N2 [28]. (51173157), and Natural Science Foundation of Zhejiang Province
(Y4100314).

with pure IPC, the decrease of G′ for IPC1 becomes more

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