polymers

Article
Toughened High-Flow Polypropylene with
Polyolefin-Based Elastomers
Xiong Wang 1, *,† , Sheng Hu 2,† , Yi Guo 1 , Guangquan Li 1 and Renwei Xu 1
1 Lanzhou Petrochemical Research Center, Petrochemical Research Institute, PetroChina, Lanzhou 730060,
China; guiyi2@petrochina.com.cn (Y.G.); liguangquan@petrochina.com.cn (G.L.);
xurenwei@petrochina.com.cn (R.X.)
2 College of Chemical and Chemical Engineering, Xi0 an Shiyou University, Xi’an 710065, China;
husheng0927@126.com
* Correspondence: wangxiong1@petrochina.com.cn
† Xiong Wang and Sheng Hu contribute equally to this article.




Received: 14 October 2019; Accepted: 28 November 2019; Published: 1 December 2019


Abstract: Polyolefin is the most widely used and versatile commodity polymer. In this work, three types
of polyolefin-based elastomers (PBEs) were adopted to toughen a high-flow polypropylene to improve
its overall performance. The chain microstructures of these PBEs, including ethylene/1-octene (E/O)
random copolymer from Dow Chemical0 s polyolefin elastomer (POE), olefin block copolymers (OBCs)
of E/O from Dow, and ethylene/propylene random copolymer from ExxonMobil’s propylene-based
elastomer, were elucidated by GPC, 13 C NMR, TREF, and DSC techniques. The mechanical, thermal
and optical properties, and morphology analysis of the PP/PBE blends were also studied to investigate
the toughening mechanism of these PBEs. The results showed that all three types of PBEs can effectively
improve the Izod impact strength of the PP/PBE blends by the addition of the rubber compositions, at
the cost of the stiffness. PBE-1 and PBE-2 were found to have a great stiffness–toughness balance with
about 1700 MPa of flexural modulus, about 110 ◦ C of HDT and 3.6 kJ/m2 of impact strength on the
prepared PP/PBE blends by forming separated rubber phase and refined spherulite crystals. As a result,
the OBC with alternating hard and soft segments could achieve a similar toughening effect as the E/P
random copolymer. Surprisingly, no obvious rubber phase separation was observed in the PP/PBE-4
blend, which might be due to the good compatibility of the E/P random chains with the isotactic PP;
therefore, the PP/PBE blend obtains great toughness performance and optical transparency with the
highest Izod impact strength of 4.2 kJ/m2 and excellent transparency.

Keywords: polypropylene; polyolefin-based elastomer; polyolefin elastomer (POE); olefin block

copolymer (OBC); propylene-based elastomer; toughening effect

1. Introduction
Polyolefins are the most widely used and versatile commodity polymers, and their properties vary
from plastic to elastomer [1–4]. Since the discovery of Ziegler-Natta catalysts for olefin polymerization
in the 1950s, the production of polyolefins with various chain microstructures and properties has
continuously grown with rapid development of catalyst technology combined with polymerization
process innovation [5–14].
Polypropylene is undoubtedly one of the most robust material fields in the polyolefin production
and consumption market globally [15–18], with a current annual demand of about 56 million tons
in 2016 [19]. They are used in a wide range of applications ranging from packaging to lightweight
engineering plastics for automobile, electrical and electronics, construction, medical, equipment, and
facilities industries [20,21]. China now possesses the largest market share in PP production of above

Polymers 2019, 11, 1976; doi:10.3390/polym11121976 www.mdpi.com/journal/polymers

Polymers 2019, 11, 1976 2 of 14

22 million tons. Due to rapid market expansion of takeout for dining box and automobile industries in
China, the high-flow homo polypropylene market has also witnessed a dramatic increase to about
above 600 kilotons annually in the recent few years.
Although the high-flow homo polypropylene with high melting index (typically above 50 g/10 min)
and good processability possesses high flexural modulus, the impact strength is relatively low compared
to the ethylene/propylene copolymer and easily suffers from brittle fracture [22]. In order to solve this
problem, two approaches are typically adopted to improve the overall performance of the polymer.
One alternative is to introduce an extra operation line for the incorporation of a small amount of
ethylene into the isotactic chain in the PP production facility, and the other method is to make
post-modifications of the high-flow polypropylene by blending elastomer with PP, and glass fibers for
automobiles [23–25].
The Polyolefin-based elastomers (PBEs) have received considerable attention because of their low
density, recycling potential, better chemical resistance, processing advantages, and good resilience
without permanent deformation. Unlike rubber, they do not require vulcanization. In addition, the
low cost together with the wide availability of ethylene, propylene and α-olefin monomers makes the
polyolefin-based elastomers more desirable. The ethylene/1-octene random copolymers (POEs) are a
typical class of PBEs, and they are produced by Dow Chemical0 s constrained geometry catalyst (CGC)
metallocene catalysts in a solution process. Due to the single-site nature of CGC, they have a much
narrower short chain branching (SCB) distribution than the Ziegler-Natta catalysts. In contrast, Exxon
has developed the propylene-based ethylene/propylene elastomers using metallocene catalysts by the
Exxpol™ technology.
Recently, ethylene/1-octene multiblock copolymer (OBC) has been commercialized successfully
using Dow Chemical0 s chain shuttling polymerization technique. The chain shuttling polymerization
employs two post-metallocene catalysts screened by high through-put technology and a chain shuttling
agent, and the two catalysts have totally different incorporation abilities of α-olefin, thus producing
different chain block, soft and hard PE segments, by a chain shuttling agent (diethyl zinc), and the
produced chains are composed of at least two alternating soft and hard segments [8,26]. This type of
multiblock chain structure gives the materials better elasticity at high temperature than their random
counterparts [27].
In this work, a comparative analysis on the microstructures of these polyolefin-based elastomers
was made by GPC, 13 C NMR and TREF techniques. Then the toughening effects of these PBEs in the
PP/PBE blends were investigated to evaluate the overall performance and toughening mechanism.
A stiffness–balance–transparency relationship among the PP/PBE blends was established by the
mechanical and thermal properties and the crystalline and rubber phase structure analysis.

2. Materials and Method

2.1. Materials
High-flow homopolypropylene (H9018H) provided by Lanzhou Petrochemical Company
(PetroChina, Lanzhou, China) was employed in this work. Three types of polyolefin-based elastomers
(PBE) for toughening were used to blend with homo-PP, including one POE sample, two OBC samples
and one propylene-based elastomer sample. The POE (ENGAGE 8200) was purchased from a distributor
of Dow Chemical (SCG Chemicals, Bangkok, Thailand) and two OBCs (INFUSE 9100 and 9500) were
purchased from Dow Chemical (Midland, Michigan, USA) as pellets, and the PBE (Vistamaax 6202)
was purchased from ExxonMobil Company (Singapore) as pellets. Engage 8200 is an ethylene/1-octene
random copolymer produced by constrained geometry catalyst (CGC) technique from Dow Chemical
and designated as PBE-1. Infuse 9100 and 9500 are ethylene/1-octene multiblock copolymers produced
by Dow Chemical0 s Chain Shuttling Polymerization technique [5,6], and are designated as PBE-2 and
PBE-3, respectively. Vistamaxx 6202, designated as PBE-4, is an ethylene/propylene random copolymer
produced by ExxonMobil0 s metallocene catalyst technique.
Polymers 2019, 11, 1976 3 of 14

2.2. Sample Preparation

The PP/POE, PP/OBC and PP/PBE (90/10 weight percent for all samples) blends were extruded at
190 ◦ C using a twin screw extruder (ZSE-34, LEISTRTIZE, Wiesbaden, Germany). The roller speed
was 80 rpm and the feed speed was set as 20%. Standard testing specimens for notched Izod impact,
flexural and tensile tests were prepared by an UN-100 Injection machine (Liuzhou Injection Molding
Machinery, Liuzhou, China) at an injection temperature of 200 ◦ C, mold temperature of 40 ◦ C and
injection pressure of 25 MPa. The PP testing samples were also prepared in the same procedure
for comparison.

2.3. Characterization

2.3.1. Mechanical Test

The notched Izod impact test was conducted on 23 ◦ C and on a 92T Pendulum impact tester
(TINIUS OLSEN, Philadelphia, PA, USA) with a hamper energy of 2.0103 kJ/m2 according to GB/T
1843-2008. An Instron 5566 universal testing machine (Instron, Norwood, MA, USA) was used to test
the tensile and flexural performances at room temperature (23 ◦ C) according to standards of GB/T
1040.1-2006 and GB/T 9341-2008, respectively. The melting index was conducted on a CEAST 7028
(CEAST, Turin, Italy) according to GBT 3682, and the heat distortion temperature is tested on XRW-300
(Jingjianjiance, Chende, China) according to GB/T 1634.1-2004. Before the test, all test specimens were
kept in 23 ◦ C for 24 h, and the test result was an average value.

2.3.2. GPC and 13 C NMR Analysis

Gel permeation chromatography (GPC) was conducted in a GPC-IR instrument (Polymer Char,
Valencia, Spain) using 1,2,4-trichlorobenzene as a solvent at 135 ◦ C with a sampling concentration of
3 mg/mL and a sampling rate of 1.0 mL/min. 13 C NMR spectra of samples were performed on a Bruker
(Breika, Massachusetts, USA) 500 MHz at 120 ◦ C using o-C6 H4 Cl2 /o-C6 D4 Cl2 (50% v/v) as a solvent
in a 10-mm tube. The spectra of the quantitative 13 C NMR were obtained with a 74◦ flip angle, an
acquisition time of 1.5 s, and a delay of 4.0 s.

2.3.3. DSC and XRD Analysis

Differential scanning calorimetry (DSC) measurements were performed on a DSC 214 Polyma
instrument (NETZSCH, Selb, Germany). In order to eliminate the heat history of the sample, a 7-mg
sample was heated from room temperature to 200 ◦ C under nitrogen protection at a heating rate of
30 ◦ C /min, then cooled to 30 ◦ C at a cooling rate of 20 ◦ C /min. The melting curves were obtained
when heating the samples to 200 ◦ C at the same heating rate once again, and crystallization curves were
recorded when cooling the samples to 30 ◦ C. Wide-angle X-ray diffraction (WXRD) was performed on
a D8 ADVANCE diffractometer (Bruker, Karlsruher, Germany) using a 1-mm-thick sheet of samples.
The samples were scanned at 40 ◦ C and 4◦ /min under Cu-Kα irradiation (λ = 0.154 nm).

2.3.4. TREF
Temperature rising elution fractionation (TREF) was carried out in a model 200+ instrument
(Polymer Char, Spain). Standard Conditions were used in all analyses with 40 mg in 20 mL of
1,2,4-trichlorobenzene (TCB), 0.3 mL analysis sample volume, crystallization rate of 0.5 ◦ C/min, and
elution rate of 1 ◦ C/min.

2.3.5. Morphology Observation

Isothermal crystallization was observed using a polarized optical microscope, (DM2500P, Leica,
Weztlar, Germany). The specimens for SEM observation were prepared by the cryogenic fracture of the
injection molded bars under liquid nitrogen for 15 min and then etched in xylene at room temperature
Weztlar, Germany). The specimens for SEM observation were prepared by the cryogenic fracture of
the injection molded bars under liquid nitrogen for 15 min and then etched in xylene at room
temperature for 24 h for rubber phase removal. The fracture surface morphology was observed on a
ULTRA plus field-emission electron microscope (FESEM, Zeiss, Oberkochen, Germany), after being
coated with a thin layer of gold-palladium in vacuum.
Polymers 2019, 11, 1976 4 of 14

3. Results and Discussion

for 24 h for rubber phase removal. The fracture surface morphology was observed on a ULTRA plus
3.1. Polyolefin-based Elastomers
field-emission electron microscope (FESEM, Zeiss, Oberkochen, Germany), after being coated with a
thinThe
layer of gold-palladium
high temperature GPCin vacuum.
was used to determine their molecular weights (Mw and Mn) and
polydispersity index (PDI). We can see from the GPC elution curves (Figure 1) that the ethylene/1-
3. Results
octene randomandcopolymer
Discussion(PBE-1) has the longest elution time which means it has the lowest average
molecular weight compared to other elastomers. The average molecular weight of the propylene-
3.1. Polyolefin-Based Elastomers
based ethylene/propylene copolymer (PBE-4) is close to that of PBE-1. Due to the single-site nature
The highcatalysts,
of metallocene temperature GPC
PBE-1 andwas used
PBE-4 to determine
have a narrowertheir molecular
molecular weights
weight (Mw and
distribution Mnto
(close ) and
2)
polydispersity
compared index (PDI).Z-N
to conventional We can see from
catalysts. theolefin
The GPC elution curves
multiblock (Figure 1) that
copolymers the and
PBE-2 ethylene/1-octene
PBE-3 have
random
shorter copolymer
elution (PBE-1)
times and, has thehave
therefore, longest elution
a much time
higher which means
molecular weight.it Via
has the
thechain
lowest average
shuttling
molecular weight compared to other elastomers. The average molecular weight of the propylene-based
polymerization techniques in a continuous process, the molecular weight distributions of PBE-2 and
ethylene/propylene
PBE-3 can also obtaincopolymer (PBE-4) isclose
narrow distribution closetotoSchulz-Flory
that of PBE-1. Due to the
distribution (Mwsingle-site nature of
/Mn = 2) compared
metallocene catalysts, PBE-1 and PBE-4 have a narrower molecular weight distribution (close
to other multi-sites Z-N catalysts, with 2.9 and 2.7 of PDI, respectively [8,28,29]. The molecular weight to 2)
compared to conventional Z-N
and PDI data are listed in Table 1. catalysts. The olefin multiblock copolymers PBE-2 and PBE-3 have
shorter elution times and, therefore, have a much higher molecular weight. Via the chain shuttling
polymerization techniques in a continuous process, the molecular weight distributions of PBE-2 and
PBE-3 can also obtain narrow distribution close to Schulz-Flory distribution (Mw /Mn = 2) compared to
other multi-sites Z-N catalysts, with 2.9 and 2.7 of PDI, respectively [8,28,29]. The molecular weight
and PDI data are listed in Table 1.

Figure 1. GPC molecular weight distribution comparison of Polyolefin-based elastomers.

Figure 1. GPC molecular weight distribution comparison of Polyolefin-based elastomers.
Table 1. Characteristics of the used polyolefin-based elastomers.

Entry Sample Mol% a Comon. Mw b (kg/mol) M n (kg/mol) PDI

1 PBE-1 12.2 (1-octene) 74.2 31.7 2.3
2 PBE-2 18.2 (1-octene) 178.2 62.1 2.9
3 PBE-3 15.1 (1-octene) 138 51.6 2.7
4 PBE-4 16.5 (ethylene) 89.2 38.7 2.3
a Molar fraction of comonomers in elastomers determined by NMR; b Determined by GPC.

As shown in Table 1, comonomers content in the polyolefin-based elastomers do not vary much,
roughly from 12% to 18%, with 12.2% 1-octene in the ethylene/1-octene random copolymer (PBE-1),
18.2% and 15.1% 1-octene in the olefin multiblock copolymers PBE-2 and PBE-3, respectively, and
16.5% ethylene in the propylene-based ethylene/propylene copolymer (PBE-4). The microstructure
differences of the PBEs could be more clearly exhibited from the 13 C NMR results in Figure 2 and
Table 2. Table 2 provides the sequence fractions of the polyolefin-based elastomers obtained from the
13 C NMR spectra [30–33]. From the NMR results, there is no OOO triad sequence detected in PBE-1,
18.2% and 15.1% 1-octene in the olefin multiblock copolymers PBE-2 and PBE-3, respectively, and
16.5% ethylene in the propylene-based ethylene/propylene copolymer (PBE-4). The microstructure
differences of the PBEs could be more clearly exhibited from the 13C NMR results in Figure 2 and
Table 2. Table 2 provides the sequence fractions of the polyolefin-based elastomers obtained from the
13C NMR spectra [30–33]. From the NMR results, there is no OOO triad sequence detected in PBE-1,
Polymers 2019, 11, 1976 5 of 14
PBE-2 and PBE-3. Only a small amount of OO diad sequence about 0.8% exist in ethylene/1-octene
copolymers PBE-1 and PBE-3, and PBE-2 has about 1.6% OO diad sequence.
PBE-2 and PBE-3. Only a small amount of OO diad sequence about 0.8% exist in ethylene/1-octene
copolymers PBE-1 and PBE-3, and PBE-2 has about 1.6% OO diad sequence.

Figure 2. 13 C NMR spectrum of polyolefin-based elastomers measured at 120 ◦ C using o-C6 H4 Cl2 /o-C6 D4 Cl2
Figure 2. 13as
(50% v/v) C NMR spectrum of polyolefin-based elastomers measured at 120 °C using o-C6H4Cl2/o-
the solvent.
C6D4Cl2 (50% v/v) as the solvent.
Table 2. The triad and diad distributions of ethylene/1-octene and ethylene/propylene copolymers
obtained by 13 C NMR.

EEO + EOO + EO +
EEE OEO/PEP EOE/EPE OOO/PPP OO/PP
Sample OEE/EEP OOE/EPP EE (%) OE/EP
(%) (%) (%) (%) (%)
+ PEE (%) + PPE (%) + PE (%)
PBE-1 66.05 20.66 1.62 10.08 1.59 0 76.38 22.82 0.80
PBE-2 54.27 21.76 6.03 14.67 3.27 0 65.15 33.12 1.63
PBE-3 60.26 20.54 3.41 14.25 1.54 0 70.53 28.7 0.77
PBE-4 0.03 4.25 11.31 2.76 25.13 56.52 2.15 28.77 69.08

Along the NMR, TREF is a useful tool to compare the molecular chain microstructure of these
PBEs. As seen from the TREF curves (Figure 8a), the PBE-1 and PBE-4 are typical ethylene/1-octene or
ethylene/propylene random copolymers with a major soluble peak, while PBE-2 and PBE-3 are typical
olefin block copolymer with characteristic multiblock peaks around 80–100 ◦ C, which is different from
linear low density polyethylene (LLDPE) or high density polyethylene (HDPE), apart from the soluble
peaks. Comparing the two OBCs (PBE-2 and PBE-3), we found out that PBE-3 has higher soluble
fraction than PBE-2 with less 1-octene content, and that could be explained by a higher content of
multiblock peaks around 80–100 ◦ C of PBE-2 observed in TREF curves.

3.2. PP/Polyolefin-Based Elastomer Blends

Three types of polyolefin-based elastomers including POE (PBE-1), OBC (PBE-2 and PBE-3) and
propylene-based ethylene-propylene copolymer (PBE-4) were used to blend with polypropylene.
The molecular structures of the three elastomers are shown in Figure 3. The molecular chain structure
of OBC consists of hard and soft segments with different lengths, while the whole molecular chain of
POE and propylene-based elastomer mainly consists of soft segments, which can be etched by xylene
in room temperature and shown as the rubber phase in the PP/PBE blend.
 Three types of polyolefin-based elastomers including POE (PBE-1), OBC (PBE-2 and PBE-3) and
propylene-based ethylene-propylene copolymer (PBE-4) were used to blend with polypropylene. The
molecular structures of the three elastomers are shown in Figure 3. The molecular chain structure of
OBC consists of hard and soft segments with different lengths, while the whole molecular chain of
Polymers
POE and 2019, 11, x FOR PEER REVIEW
propylene-based 7 of 16
elastomer mainly consists of soft segments, which can be etched by xylene
Polymers 2019, 11, 1976 6 of 14
in room temperature and shown as the rubber phase in the PP/PBE blend.
increase; and PBE-4 increased the impact strength to 4.2 kJ/m2, a dramatic 110% increase. The different
toughening effects could be due to the different molecular chain structures as seen in Figure 3.

Table 3. Mechanical analysis results of the PP and PP/PBE blends.

Elongatio Haze (1 Xc,

Melting Flexural Tensile
n at Impact HDT mm WAXD
Entry f Sample Index Modulus Yield
Stress Break Strengt Sheet) %
h kJ/m 2 °C
g/10 min MPa MPa % %

5 3. Scheme
Figure PP of molecular
73 chain 1850 37.8structure8.1
and aggregation 2.0 119 elastomer
of PP/polyolefin-based 71 blends.
63.6
Figure 3. Scheme of molecular chain and aggregation structure of PP/polyolefin-based elastomer
blends.
6 PP/PBE-1 53 1690 35.5 14.1 3.6 112 83 60.9
To evaluate the overall performance of these PBEs, the mechanical and optical properties of the
PP and PP/PBE blends were tested, and the results are shown in Table 3. From Table 3, we can see
To7evaluatePP/PBE-2
the overall53 performance1680 of these 35.5PBEs, the 10.2
mechanical 3.6 and 109 98
optical properties 59.3of the
the three types of PBEs take a different blending effect on the PP/PBE blends. On one hand, all three
PP and PP/PBE blends were tested, and the results are shown in Table 3. From Table 3, we can see
PBEs have 8 a positive
PP/PBE-3consequence 55 on1750 36.8 effect
the toughening 9.3of the PP/PBE
3.0 113
blends at99the cost62.1 of the
the three types of PBEs take a different blending effect on the PP/PBE blends. On one hand, all three
stiffness of the blends. The flexural modulus of the PP is the highest at 1850 MPa, while the impact
PBEs have 9 a PP/PBE-4
positive consequence54 on the toughening
1350 33.0 effect
12.7of the PP/PBE
4.2 blends
96 at57the cost of the
58.8
strength is the lowest at 2.0 kJ/m2 . Therefore, there is a need to toughen PP to improve the overall
stiffness of the blends. The flexural modulus of the PP is the highest at 1850 MPa, while the impact
performance
f. PP/PBE of (1/2/3/4)
the finalsamples
PP product.
were As seen
mixed from Figure
and there
melting 4, all ofPP the four(1/2/3/4)
PBEs have efficiently
strength is the lowest at 2.0 kJ/m 2. Therefore, is aextruded
need toontoughen to PBEPP to improve weight theratio 90:10,
overall 2
improved the toughness of PP blends. PBE-3 (OBC) raised the impact strength
respectively. of the final PP product. As seen from Figure 4, all of the four PBEs have efficiently from 2.0 to 3.0 kJ/m
performance 2
with a 50% increase; PBE-1 (POE) and PBE-2 (OBC) increased the impact strength to 3.6 kJ/m , an 80%2
improvedAsand the the
for toughness of PP blends. PBE-3 the(OBC) raised 2the impact strengthbetween
from 2.0 stiffness
to 3.0 kJ/m
increase; PBE-4overall
increasedperformance
the impact of strength final PP
to 4.2 product,
kJ/m the balance
, a dramatic 110% increase. The differentand
with a 50%
toughness increase;
needs to PBE-1
be taken(POE)
into and PBE-2 (OBC)
consideration. increased
Despite the the impact
excellent strength
toughening to 3.6
effectkJ/m
of
2, an 80%
PBE-4, the
toughening effects could be due to the different molecular chain structures as seen in Figure 3.
flexural modulus and the heat distortion temperature decreased rapidly at the same time. It would
not be sufficient for use 3.asMechanical
Table a heat-resistant
analysisfood container
results of the PPwith 1540 MPa
and PP/PBE of flexural modulus and
blends.
96 °C of HDT. By the same token, the 3.0 kJ/m2 of impact strength for PBE-3 might not be good enough
Melting Flexural Tensile Elongation Impact Haze Xc,
for impact
Entry resistance.Index
f Sample The PBE-1 and PBE-2
Modulus Yieldhave aatgoodBreak balance between
Strength
HDT stiffness and toughness
(1 mm WAXD
◦C
with about 1700 MPa g/10flexural
min modulus,
MPa about
Stress MPa110 °C % HDT and kJ/m23.6 kJ/m2 impact Sheet)strength,
% %which
would
5 be suitable
PP for the
73 use mentioned
1850 above.
37.8 8.1 2.0 119 71 63.6
6 The tensile
PP/PBE-1yield stress
53 1690PBEs has
of the 35.5a similar14.1trend to the 3.6 flexural 112 modulus 83 on the60.9 PP/PBE
7 PP/PBE-2 53 1680 35.5 10.2 3.6 109 98 59.3
blends
8
as seen
PP/PBE-3
in Table 55
3. The increases
1750
of the
36.8
elongation
9.3
at break
3.0
are mainly
113
due to
99
the addition
62.1
of
the9polyolefin-based
PP/PBE-4 elastomers
54 containing33.0
1350 soft segment 12.7 molecular 4.2 chains. 96 57 58.8
f PP/PBE (1/2/3/4) samples were mixed and melting extruded on PP to PBE (1/2/3/4) weight ratio 90:10, respectively.

Figure 4. The notch Izod impact strength for PP and PP/PBE blends tested at 23 ◦ C.

As for the Figure

overall4.performance
The notch Izod impact strength for PP and PP/PBE blends tested at 23 °C.
of the final PP product, the balance between stiffness and toughness
needs to be taken into consideration. Despite the excellent toughening effect of PBE-4, the flexural
On the other hand, the optical properties sometimes also need to be taken into account for the
modulus and the heat distortion temperature decreased rapidly at the same time. It would not be
appearance aspect. The haze results are list in table 3. Although PBE-1 and PBE-2 have a◦ great
sufficient for use as a heat-resistant food container with 1540 MPa of flexural modulus and 96 C of
stiffness–toughness balance on the final PP/PBE blends, the optical properties, especially the haze,
Polymers 2019, 11, 1976 7 of 14

HDT. By the same token, the 3.0 kJ/m2 of impact strength for PBE-3 might not be good enough for
impact resistance. The PBE-1 and PBE-2 have a good balance between stiffness and toughness with
about 1700 MPa flexural modulus, about 110 ◦ C HDT and 3.6 kJ/m2 impact strength, which would be
suitable for the use mentioned above.
The tensile yield stress of the PBEs has a similar trend to the flexural modulus on the PP/PBE
blends as seen in Table 3. The increases of the elongation at break are mainly due to the addition of the
polyolefin-based elastomers containing soft segment molecular chains.
On the other hand, the optical properties sometimes also need to be taken into account for the
appearance aspect. The haze results are list in Table 3. Although PBE-1 and PBE-2 have a great
Polymers 2019, 11, x FOR PEER REVIEW 8 of 16
stiffness–toughness balance on the final PP/PBE blends, the optical properties, especially the haze,
increased
increased notoriously
notoriouslyfrom from71%71%to 83%to and
83%98% respectively,
and causing badcausing
98% respectively, transparency. Furthermore,
bad transparency.
the PBE-3 also has a similar influence on the PP/PBE-3 blend as it has
Furthermore, the PBE-3 also has a similar influence on the PP/PBE-3 blend as it has the samethe same type of elastomer
type asof
PBE-2 (OBC), resulting in an opaque appearance with 99% of haze. In contrast,
elastomer as PBE-2 (OBC), resulting in an opaque appearance with 99% of haze. In contrast, PBE-4 PBE-4 has the best
effect
has the onbest
the transparency of the PP/PBEof
effect on the transparency blends, decreasing
the PP/PBE the decreasing
blends, haze from 71% to 57%,
the haze despite
from 71% leading
to 57%,
to bad stiffness.
despite leading to bad stiffness.
The
The transparency comparison can
transparency comparison can be
be clearly
clearly illustrated
illustrated from
from the the digital
digital photos
photos ofof the
the PP/PBE
PP/PBE
blends in Figure 5. The text can be read from the 2-mm PP sheet, it is illegible
blends in Figure 5. The text can be read from the 2-mm PP sheet, it is illegible from the PP/PBE-1from the PP/PBE-1 sheet,
and it is hard to identify for the PP/PBE-2 sheet, while the PP/PBE-4 provided
sheet, and it is hard to identify for the PP/PBE-2 sheet, while the PP/PBE-4 provided a higher a higher resolution
for the text.for
resolution Forthe
thistext.
reason,
For the
thisPP/PBE-4
reason, theblends would blends
PP/PBE-4 be an excellent
would be material for transparent
an excellent materialand for
impact-resistant use, if not used in relatively high temperatures.
transparent and impact-resistant use, if not used in relatively high temperatures.

(a) PP;
Figure 5. Digital photos of transparency comparison of PP and PP/PBE blends of 2-mm sheet. (a)
(b) PBE-1; (c) PBE-2; (d) PBE-4.
PBE-2; (d) PBE-4.

3.3. XRD Analysis

3.3. XRD Analysis
Wide angle X-ray diffraction analysis were conducted to analyze the PP crystal type and content.
Wide angle X-ray diffraction analysis were conducted to analyze the PP crystal type and content.
From Figure 6, the typical diffuse peaks of α crystal of PP can be observed with the 2θ of 14.1◦ , 16.8◦ and
From Figure 6, the typical diffuse peaks of α crystal of PP can be observed with the 2θ of 14.1°, 16.8°
◦ , which are attributed to the (110), (040) and (130) crystal faces, respectively, and these peaks also
18.6
and 18.6°, which are attributed to the (110), (040) and (130) crystal faces, respectively, and these peaks
appears
also appearsin theinother four PP/PBE
the other blendsblends
four PP/PBE indicating that thethat
indicating major
thePP crystal
major PPtype is αtype
crystal crystal.
is αThe tiny
crystal.
characteristic peaks of β crystal could be seen in PP and the four PP/PBE blends with slight
The tiny characteristic peaks of β crystal could be seen in PP and the four PP/PBE blends with slight peaks either
around 16.1◦around
peaks either or 21.1◦16.1°
, which contribute
or 21.1°, whichto the (300) to
contribute andthe(301)
(300)crystal faces,
and (301) respectively,
crystal indicating
faces, respectively,
that PP andthat the PP/PBE ◦
indicating PP andblends containblends
the PP/PBE slight βcontain
crystals.slight
The peak around The
β crystals. 20.5 peak
is unobserved, which
around 20.5° is
shows that the γ crystal in PP and PP/PBE blends could be neglected.
unobserved, which shows that the γ crystal in PP and PP/PBE blends could be neglected.
The relative crystallinity index from WAXD of PP and the PP/PBE blends were calculated in
Table 3. The crystallinity of PP is 63.6%, followed by PP/PBE-3 of 62.1%, PP/PBE-1 of 60.9%, PP/PEB-
2 of 59.3%, and PP/PBE-4 of 58.8%. The stiffness (Flexural modulus and HDT) of PP and PP/PBE
blends are roughly in accordance with the crystallinity of the polymers. It would make sense that
crystal content is linear to stiffness with α formation as a major crystal. The polyoelfin-based
 Polymers 2019, 11, x FOR PEER REVIEW 9 of 16
Polymers 2019, 11, 1976 8 of 14

Polymers 2019, 11, x FOR PEER REVIEW 9 of 16

Figure 6. XRD of PP and PP/PBE blends.

Figure 6. XRD of PP and PP/PBE blends.
The relative crystallinity index from WAXD of PP and the PP/PBE blends were calculated in
Table3.4.3.DSC
TheAnalysis
crystallinity of PP is 63.6%, followed by PP/PBE-3 of 62.1%, PP/PBE-1 of 60.9%, PP/PEB-2
of 59.3%,Asand PP/PBE-4
is well known,of 58.8%. The stiffness
the thermal properties(Flexural modulus
are strongly andwith
related HDT)theofcrystallinity
PP and PP/PBEof theblends
are materials
roughly and their microstructure.
in accordance with theThe DSC thermal
crystallinity analysis
of the was carried
polymers. out to make
It would exhibitsense
the melting
that crystal
and crystalline
content is linear tobehavior.
stiffnessAs seenαfrom
with Figure as
formation 7a.,athe melting
major curveThe
crystal. of PP/PBE-2 has two peaks.
polyoelfin-based The used
elasomers
peak around 166 °C is attributed to the melting peak of the isotactic homo-PP,
in the PP/PBE blends make the PP spherulite size smaller as seen in the polarized optical microscope, and the other
distinctive peak is due to the crystalline
Figure 6.part
XRD ofofOBC
PP containing
and PP/PBE both hard and soft segments in the
blends.
and thus decrease the crystallinity of PP; we will discuss the factor of crystal size in the morphology
molecular chain, with the melting peak around 117 °C for the PP/PBE-2 blend. However, only one
section later.
3.4.peak
DSCwas visible in the PP/PBE-3; the absence of the minor peak around 120 °C from the characteristic
Analysis
melting peak of OBC might be due to the relatively low content of the soft-hard segment alternating OBC
3.4. DSC
As is Analysis
well known, the thermal properties are strongly related with the crystallinity of the
chain (see the evidence from TREF results). From Figure 7b, a slightly shift to the right or a higher
materials and known,
temperature
As is well their
rangemicrostructure.
ofthe
the thermal TheofDSC
starting point thermal
crystallization
properties are stronglyanalysis
relatedwas
temperature withTcarried
c (onset) out
cantobeexhibit
the crystallinitynoticed the
of thewithmelting
materials
andthe PP/PBE
crystalline blends compared
behavior. As seento PP,
from signifying
Figure that
7a., the the nucleating
melting curve speed
and their microstructure. The DSC thermal analysis was carried out to exhibit the melting andof of
PP/PBE-2 the PP
has spherulite
two peaks. The
increased
peak around
crystalline and crystal
166 °C
behavior. size
Asisseen became
attributed smaller
from Figure when
to the the
7a.,melting polyolefin-based
peakcurve
the melting of the elastomers were
isotactic homo-PP,
of PP/PBE-2 used.
has two peaks.and The
the peak
other
around 166 ◦peak
distinctive is due to the
C is attributed crystalline
to the part of
melting peak of OBC containing
the isotactic both hard
homo-PP, and theandother
soft distinctive
segments in the
peak
molecular chain, with the melting peak around 117 °C for the PP/PBE-2
is due to the crystalline part of OBC containing both hard and soft segments in the molecular chain, blend. H owever, only one
peakthe
with wasmelting
visible peak
in thearound
PP/PBE-3; ◦ C for
117 the absence of the minor
the PP/PBE-2 blend. peak around 120
However, only°C onefrom
peakthewas
characteristic
visible in
melting
the peak ofthe
PP/PBE-3; OBC might of
absence bethe
dueminor
to the peak
relatively low 120
around ◦ C from
content of thethesoft-hard segmentmelting
characteristic alternating
peakOBC
of
chain (see the evidence from TREF results). From Figure 7b, a slightly shift
OBC might be due to the relatively low content of the soft-hard segment alternating OBC chain (see the to the right or a higher
temperature
evidence fromrange
TREFof the starting
results). From point
Figureof7b,crystallization
a slightly shifttemperature
to the right or Tc a(onset)
highercan be noticedrange
temperature with
the PP/PBE blends compared to PP, signifying that the nucleating speed
of the starting point of crystallization temperature Tc (onset) can be noticed with the PP/PBE blends of the PP spherulite
increased and
compared crystal
to PP, size became
signifying that thesmaller whenspeed
nucleating the polyolefin-based
of the PP spherulite elastomers
increasedwereand used.
crystal size
became smaller when the polyolefin-based elastomers were used.

Figure 7. DSC curves of PP and PP/PBE blends. (a) melting curves; (b) cooling curves.

The melting temperature Tm, crystallization temperature Tc and the melting enthalpy of PP and
the PP/PBE blends from DSC analysis results are shown in Table 4. The crystallization peak of PP and
the PP/PBE blends are around 126 °C, and the melting endothermic enthalpy of the PP/PBE blends

Figure 7. DSC curves of PP and PP/PBE blends. (a) melting curves; (b) cooling curves.
Figure 7. DSC curves of PP and PP/PBE blends. (a) melting curves; (b) cooling curves.

The melting temperature Tm, crystallization temperature Tc and the melting enthalpy of PP and
the PP/PBE blends from DSC analysis results are shown in Table 4. The crystallization peak of PP and
the PP/PBE blends are around 126 °C, and the melting endothermic enthalpy of the PP/PBE blends
Polymers 2019, 11, x FOR PEER REVIEW 10 of 16

diminishes in contrast to PP. The melting endothermic enthalpy ΔHm can be used to calculate the
relative crystallinity Xc, thus the value of ΔHm is a direct indication of the degree of crystallinity with
Polymers 2019, 11, 1976 9 of 14
the highest Xc for the PP/PBE-3 and the lowest Xc for PP/PBE-4. This melting enthalpy comparison of
these materials is similar to the trend in the XRD results.
The melting temperature Tm , crystallization temperature Tc and the melting enthalpy of PP and
the PP/PBE blends from DSC analysisTable 4. DSC
results analysisinresults.
are shown Table 4. The crystallization peak of PP and
◦
the PP/PBE blends are around 126 C, and theTcmelting (Onset)endothermic
Tc endothermic Tm ∆H can
enthalpy
ΔHm of the PP/PBE blends
diminishes in contrastSample
to PP. The melting enthalpy m be used to calculate the
(Peak)
relative crystallinity Xc , thus the value °C is a°C
of ∆H direct (peak) °C of the degree
indication J/g of crystallinity with
m
the highest Xc for the PP/PBE-3 and the lowest Xc for PP/PBE-4. This melting enthalpy comparison of
PP 126.2 130.7 165.3 151.4
these materials is similar to the trend in the XRD results.
PP/PBE-1 126.8 131.3 165.7 134.4
Table 4. DSC analysis results.
PP/PBE-2 126.7 131.4 165.8 129.3
Sample T c (Peak) ◦ C T c (Onset) ◦ C T m (Peak) ◦ C ∆H m J/g
PP PP/PBE-3
126.2 126.1 130.8
130.7 167.1 165.3 139.9 151.4
PP/PBE-1 126.8 131.3 165.7 134.4
PP/PBE-2 PP/PBE-4
126.7 126.2 131.1
131.4 165.9 165.8 128.9 129.3
PP/PBE-3 126.1 130.8 167.1 139.9
PP/PBE-4 126.2 131.1 165.9 128.9
3.5. TREF Analysis
3.5. TREF Analysis
To explore the microstructure of the polyolefin-based elastomers and the toughened PP/PBE
blends,
To explore thetechnique
the TREF was adopted
microstructure to characterize the
of the polyolefin-based Chemicaland
elastomers Composition
the toughened Distribution
PP/PBE
(CCDs) of these materials. As reasoned before, Figure 8a shows the TREF
blends, the TREF technique was adopted to characterize the Chemical Composition Distribution analysis of three types of
(CCDs) of these materials. As reasoned before, Figure 8a shows the TREF analysis of three typesa
polyolefin-based elastomers (PBE-1/PBE-2 and PBE-3/PBE-4). In the POE (PBE-1) curve, only
soluble
of fraction peakelastomers
polyolefin-based appears, which is attributed
(PBE-1/PBE-2 andtoPBE-3/PBE-4).
the ethylene/1-octene (E/O)
In the POE random
(PBE-1) copolymer.
curve, only a
While infraction
soluble addition to the
peak SF peak,
appears, extraispeaks
which in thetohigher
attributed temperature range
the ethylene/1-octene (80–100
(E/O) random °C) copolymer.
exist in the
curvesin
While ofaddition
OBCs (PBE-2
to theand PBE-3).
SF peak, Thepeaks
extra CCDsinofthe SFhigher
in OBCtemperature
are supposed to be(80–100
range similar◦ C)with thein
exist SFthe
in
the POE
curves of and
OBCs basically
(PBE-2 consist of anThe
and PBE-3). ethylene/1-octene
CCDs of SF in OBC random copolymerto(soft
are supposed segment);
be similar withthe
theCCDs
SF in
in the higher temperature are due to the molecular chain with alternating hard
the POE and basically consist of an ethylene/1-octene random copolymer (soft segment); the CCDs and soft segments
produced
in the higherby temperature
the chain shuttling
are duepolymerization
to the molecular technology.
chain withThe hard segment
alternating hard and is composed
soft segmentsof a
polyethylene
produced chain
by the withshuttling
chain a trace 1-octene comonomer,
polymerization if any The
technology. scattered in the chain,
hard segment and the of
is composed soft
a
segment as mentioned above is composed of an ethylene/1-octene random copolymer.
polyethylene chain with a trace 1-octene comonomer, if any scattered in the chain, and the soft segment Obviously,
thementioned
as chemical composition and CCDs
above is composed of anvary in the two OBCs,
ethylene/1-octene and PBE-2
random containsObviously,
copolymer. harder–softer segment
the chemical
alternating molecular
composition and CCDs chains. From
vary in the impact
the two OBCs, andtest results, we can reasonably
PBE-2 contains harder–softerinfer that thealternating
segment hard–soft
segment alternating molecular chains could possess as excellent a toughening effect
molecular chains. From the impact test results, we can reasonably infer that the hard–soft segment as the ethylene/1-
octene random
alternating molecular
molecular chain
chains could[34].possess as excellent a toughening effect as the ethylene/1-octene
random molecular chain [34].

Figure 8. TREF curves. (a) Four polyolefin-based elastomers (PBEs); (b) PP and PP/PBE blends.
Figure 8. TREF curves. (a) Four polyolefin-based elastomers (PBEs); (b) PP and PP/PBE blends.
Polymers 2019, 11, 1976 10 of 14

The third type of PBE is a propylene-based propylene/ethylene copolymer, and most

propylene/ethylene (P/E) copolymer chains are soluble, which indicates that the PBE-4 consists
basically of the E/P random copolymer. As seen in Table 5 of the TREF analysis results, PBE-4 contains
93.5% soluble fraction, and only a small part of the fractions in 58, 64 and 73 ◦ C might be ascribed to
higher molecular chain regularity of PPPP (mmm) sequence distribution, which could be discovered
in a 46.5 ppm small peak in the 13 C NMR of PBE-4 [32,33]. At the same time, the PPPPP (mmmm)
sequence in 21.8 ppm in the 13 C NMR is not observed, which is in compliance with the absence of a
peak around 120 ◦ C of isotactic PP of TREF analysis.
From Figure 8b, we can identify the highly isotactic homo-polypropylene around 122 ◦ C in PP and
the PP/PBE blends. Except for the highly isotactic PP of 87% in the homo-PP, there is a small peak of SF
of 3.1% (see Table 5) for atactic PP, and other CCDs with less regularities of PP chain structures around
52, 66 and 89 ◦ C are also listed in Table 5, despite not obviously being in these zones. The PP/PBE-1
blend has 12.6% of SF, and this value is high above the SF from PP, which is attributed to the atactic PP
and E/O random copolymer from POE. Similarly, part of the SF of the PP/PBE-2 and PP/PBE-3 blends
belong to the soluble E/O random copolymer. Moreover, the peak at 88 ◦ C in the PP/PBE-2 blends
and peaks at 87 and 93 ◦ C in the PP/PBE-3 blends are mainly due to the alternating hard and soft
segments from PBE-2 and PBE-3, respectively. As for the PP/PBE-4 blends, the E/P random copolymer
compositions account for the increased soluble fraction.

Table 5. TREF analysis results.

Soluble
Sample Item Peak 1 Peak 2 Peak 3 Peak 4
Fraction (SF)
PBE-1 T/◦ C - - - -
Area/% 100 - - - -
PBE-2 T/◦ C - - 87.7 -
Area/% 34.1 - - 65.9 -
PBE-3 T/◦ C - 86.0 94.6 -
Area/% 60.1 - 33.2 6.7 -
PBE-4 T/◦ C 58.0 64.0 73.3 94.1
Area/% 93.5 3.9 1.1 0.8 0.8
PP T/◦ C 52.2 65.9 89.3 122.0
Area/% 3.1 4.3 3.1 2.5 87.0
PP/PBE-1 T/◦ C 51.2 66.3 93.2 122.1
Area/% 12.6 1.7 1.4 2.5 81.8
PP/PBE-2 T/◦ C 50.1 73.5 88.1 121.5
Area/% 6.3 1.5 1.9 13.6 76.6
PP/PBE-3 T/◦ C 60.8 86.9 93.5 121.7
Area/% 9.8 1.9 6.9 2.5 78.9
PP/PBE-4 T/◦ C 53.1 67.6 86.8 121.6
Area/% 10.6 3.0 1.5 1.3 83.5

3.6. Morphology Analysis

In order to evaluate the toughening and optical effects of these polyolefin-based elastomers on
the PP/PBE blends, polarized optical microscope (POM) and scanning electron microscope (SEM)
analysis would be quite effective for the investigation of the crystal and rubber size. As shown in
Figures 9 and 10, the spherulite size of PP is the biggest among these materials, and the spherulite
size could be up to 10 µm; and there are seldom rubber phases in the PP matrix (the formed holes by
xylene etching as seen from the SEM images), which leads to its poor impact performance. When these
polyolefin-based elastomers were used to modify PP, the crystal size of their PP/PBE blends became
smaller, and the rubber phase can be observed evidently in the PP/PBE-1, PP/PBE-2 and PP/PBE-3
blends. That is the main reason for toughening the PP matrix.
 Polymers 2019, 11, x FOR PEER REVIEW 13 of 16

When these polyolefin-based elastomers were used to modify PP, the crystal size of their PP/PBE
Polymers 2019, 11, 1976 11 of 14
blends became smaller, and the rubber phase can be observed evidently in the PP/PBE-1, PP/PBE-2
and PP/PBE-3 blends. That is the main reason for toughening the PP matrix.

Figure 9. Polarized
Figure 9. Polarized opticaloptical microscope
microscope photosof
photos of PP
PP and
andPP/PBE
PP/PBE blends in 150in
blends °C150 ◦ C stabilizing
stabilizing for 5 min, for 5 min,
(a) PP; (b) PP/PBE-1; (c) and (d) PP/PBE-2; (e) PP/PBE-3; (f) PP/PBE-4.
(a) PP;Polymers
(b) PP/PBE-1; (c,d) PP/PBE-2; (e) PP/PBE-3; (f) PP/PBE-4.
2019, 11, 1976 12 of 15

Figure 10.Figure 10. Scanning

Scanning electron
electron microscope imaging
microscope imaging of of
PP PP
and and
PP/PBE blends; (a)
PP/PBE PP; (b) and
blends; (a) (c)
PP;PP/PBE-
(b,c) PP/PBE-1;
1; (d) PP/PBE-2; (e) and (f) PP/PBE-3; (g) and (h) PP/PBE-4.
(d) PP/PBE-2; (e,f) PP/PBE-3; (g,h) PP/PBE-4.
It would be beneficial to have a smaller crystal size for light transmission of these materials,
however, the large size of the rubber in the PP/PBE-1, PP/PBE-2 and PP/PBE-3 blends, meanwhile,
hinders the transmission of light. Generally, when the rubber size is above the wavelength of the
visible spectroscopy (roughly 400–800 nm), the transmittance of the materials will drop and the haze
will rise. In the PP/PBE-3 blend, the rubber size is up to about 2 μm, and the haze of the blend climbs
to 99%.
Polymers 2019, 11, 1976 12 of 14

It would be beneficial to have a smaller crystal size for light transmission of these materials,
however, the large size of the rubber in the PP/PBE-1, PP/PBE-2 and PP/PBE-3 blends, meanwhile,
hinders the transmission of light. Generally, when the rubber size is above the wavelength of the visible
spectroscopy (roughly 400–800 nm), the transmittance of the materials will drop and the haze will rise.
In the PP/PBE-3 blend, the rubber size is up to about 2 µm, and the haze of the blend climbs to 99%.
Surprisingly, the rubber phase by xylene etching can be rarely observed in the PP/PBE-4 blend with
less than 200 nm rubber apertures scarcely scattered in the cross section. This explains why the PP/PBE
blend has better transparency for visible spectroscopy with a smaller crystal size. Furthermore, as can
be inferred, the propylene-based E/P copolymer has good compatibility with the isotactic homo-PP
molecular chain, forming no apparent phase separation; therefore, this great compatibility also results
in a distinctive toughening effect.

4. Conclusions
The molecular chain structures of the polyolefin-based elastomers were thoroughly studied by
GPC, 13 C NMR, TREF, and DSC techniques. Despite the different microstructures, all three types
of PBEs can effectively improve the toughness of the PP/PBE blends by the addition of the rubber
compositions. PBE-1 and PBE-2 have great stiffness–toughness balance with about 1700 MPa of flexural
modulus, about 110 ◦ C of HDT and 3.6 kJ/m2 of impact strength on the prepared PP/PBE blends
by forming separated rubber phase and refined spherulite crystals. The toughening mechanism of
the PBEs were further investigated by TREF, DSC, XRD, POM, and SEM. The results showed that
the rubber size has a significant influence on stiffness and optical properties of the PP/PBE blends.
The PBE-2 with alternating hard and soft segments could achieve a similar toughening effect as the E/P
random copolymer (PBE-1) when a similar sized rubber phase was formed. Unexpectedly, no obvious
rubber phase was observed in the PP/PBE-4 blend. Due to the excellent compatibility of the E/P random
chains with the isotactic PP, the PP/PBE blend obtained great toughness performance and optical
transparency with the highest Izod impact strength of 4.2 kJ/m2 and excellent transparency. This is
significantly important for the research and development of high-performance novel PP products with
great stiffness–toughness balance or transparent and impact-resistant PP for industrial applications.

Author Contributions: Conceptualization, X.W.; formal analysis, S.H. and Y.G.; investigation, X.W. and S.H.;
project administration, G.L.; supervision, R.X.; writing—review & editing, X.W.
Funding: This work was financially supported by PetroChina Refining and Petrochemicals Company (18-LH-07-24-01).
Acknowledgments: The financial support from PetroChina Company limited is gratefully acknowledged.
The authors would like to thank Prof. Haiyang Gao from Sun Yat-Sen University (Guangzhou, China) for
conducting 13 C NMR analysis.
Conflicts of Interest: The authors declare no conflict of interest.

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