Recent advances in polyolen technology

Jinliang Qiao,
*
ab
Meifang Guo,
ab
Liangshi Wang,
ab
Dongbing Liu,
ab
Xiaofan Zhang,
ab
Luqiang Yu,
ab
Wenbo Song
ab
and Yiqun Liu
ab
Received 28th October 2010, Accepted 23rd February 2011
DOI: 10.1039/c0py00352b
Polyolen resins are the major plastics consumed in the world and are the subject of many new research
works. This review will discuss how polyolen technology has been developed in the past decade, with
particular attention to new products, catalysts, polymerization processes and additives around the
world as well as in China.
Polyolen resins, including large-volume polymers such as low
density polyethylene (LDPE), high density polyethylene
(HDPE), linear low density polyethylene (LLDPE), poly-
propylene (PP), and also high value polymers such as poly-
butene-1 and olen block copolymers etc., are the major plastics
consumed in the world. The world consumed about 260 million
tons of plastics (about 1.5 times the steel consumption in volume)
in 2007 and among them about 110 million tons were polyolen
resins. That is to say, more than 40% plastics consumed were
polyolen resins. The science and technology of polyolens are
denitely important and some of them have been reviewed.
13
In
addition to the achievement that has been previously reviewed,
scientists have done a lot of new research works on polymer
physics, polymerization, catalysts and additives related to poly-
olens in recent years. This reviewwill discuss howpolyolen has
been developed in the past 10 years, with particular attention to
new products, catalysts, polymerization processes and additives
around the world as well as in China.
1. New products
Due to its cleaner life-cycle of production, processing, applica-
tion and recycling compared with other materials, polyolen has
been considered an ideal material for various applications, such
as packaging and other disposables, agriculture, appliances,
electronics, construction, communication, automotives, etc.
Therefore, the consumption of polyolen products increases very
fast and polyolen has the largest market share among thermo-
plastics in recent years. For example, polyolen took about 65%
of the global thermoplastic market in 2000.
1
The large market
share also brings polyolen into disrepute, such as white
pollution; therefore, polyolen has to develop from two
approaches: one is to continue to replace other materials and
help the sustainable development of our society; the other is to
improve polyolen itself to make it more friendly to the envi-
ronment and human beings. Through these two approaches,
polyolen can help save energy in materials manufacturing,
forming, recycling, and product weight reduction, and reduce
hazardousness, dangerousness, emission and waste. Both new
polyolen and modied polyolen developed based on new
catalyst, new polymerization process, new additive and polymer
physics have promoted sustainable development of our society.
The new polyolens, such as soft polyolen, new PE pipe grades
and metallocene-PP have replaced many other materials; the
modied polyolen resins, such as low-soluble-fraction PP for
lm and transparent container, low VOC (volatile organic
compounds) impact PP, phthalate free PP, anti-static polyolen
and anti-bacterial polyolen with low cost have beneted our
health and environment. The reactor-made high performance
polyolen resins, such as reactor-made high melt strength PP and
special resins for automobile bumper have replaced some poly-
olen compounds.
1.1 New polyolen pipe grades
PE pipe has been recognized as the most suitable pipe for water
and gas conveyance in cities. As was conrmed in the earthquake
of Kobe of Japan in 1995, PE pipe can be much better than steel
a
Polyolen National Engineering Research Center, Beijing, 100013, China
b
SINOPEC Beijing Research Institute of Chemical Industry, Beijing,
100013, China
Jinliang Qiao
Dr Jinliang Qiao is vice presi-
dent of SINOPEC Beijing
Research Institute of Chemical
Industry and director of the
Polyolen National Engineering
Research Center. He has pub-
lished more than 70 papers and
led more than 80 patents. He
got his Bachelor degree from the
University of Science and Tech-
nology of China in 1982, Master
degree from Beijing Research
Institute of Chemical Industry in
1985 and PhD from Beijing
University in 1996.
This journal is The Royal Society of Chemistry 2011 Polym. Chem., 2011, 2, 16111623 | 1611
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pipe in earthquake. In fact, no PE pipes were broken in that
Kobe earthquake. The PE pipe is not only suitable for gas and
cold water supply, but also feasible for hot water application.
PE-RT pipe, a non-crosslinked PE pipe, grows very fast in recent
years to replace crosslinked PE pipes for hot water trans-
portation.
Several PE manufacturers can produce PE-RT resins, such as
Dow chemical company, Lyondellbasell and SK Corporation.
New generation PE-RT with specically designed molecular
structures and controlled side-chain distribution, produced by
different polymerization processes, has better high-temperature
long term hydrostatic strength. For example, DOWLEX 2388 is
an ethylene-octene copolymer produced by Dows constrained
geometry catalyst and solution process. PE-RT pipe has many
advantages, such as non-crosslinking, high exibility, excellent
weldability, and long-term application at elevated temperature.
PE-RT is a kind of environment friendly material with high
performance and low cost.
1.2 Soft PP and olen elastomer
To replace PVC (polyvinyl chloride), SBS (styrene-butadiene-
styrene block copolymer), SIS (styrene-isoprene-styrene block
copolymer), SEBS (hydrogenated styrene-butadiene-styrene
copolymer), TPVs (thermoplastic vulcanizates), etc., several soft
PPs and olen elastomers including low modulus impact PP,
stereoblock PP
4
and olen block copolymers (OBCs)
5
etc. have
been developed in recent years, and among them OBCs with the
trade name INFUSE are the most attractive.
The INFUSE OBCs were developed and manufactured by
Dow Chemical Company using a shuttling polymerization
process, which will be introduced in detail in section 2.1 of this
review. OBCs applications include exible molded goods, prole
extruded products, hoses and tubes, elastic bers and lms,
foams, adhesives and tapes. OBCs comply with all requirements
for food contact as set forth by FDA and EU. OBCs maintain
excellent exibility at much higher temperature than traditional
olen elastomers and have exceptional processibility, a similar
permanent set to SEBS and similar compression set to TPV at
70

C. Compared with traditional thermoplastic elastomers
including exible PVC, EVA (ethylene-vinyl acetate copolymer),
SEBS, SBS and SIS, OBCs have many advantages, such as
lighter weight and lower cost. Compared with other polyolen
based elastomers including TPV, polyolen elastomer (POE),
polyolen plastomer (POP) and amorphous poly-alpha-olen
(APAO), OBCs also have advantages, such as better compres-
sion set and improved processibility.
1.3 Transparent PP with low soluble fraction
The transparent PP lm and container have been used more and
more widely in food contact applications, which often require
heating with food by microwave oven. Compared with glass or
other transparent materials, transparent PP can help save energy
during the formation process, transportation and application.
However, transparent PP usually contains a high level soluble
fraction, which is detrimental to human health when the soluble
components dissolve into food. Several kinds of transparent PP
with a low soluble fraction have been developed in recent years.
The random PP copolymer made by metallocene catalyst has
a much lower soluble content compared with traditional random
PP copolymer because of its uniform co-monomer distribution.
It can be used for both food contacting lms and food
containers.
Propylene/butene-1 random copolymer usually contains less
soluble fraction than traditional propylene/ethylene random
copolymer. SINOPEC has commercialized propylene/butene-1
random copolymers by using new additives and its high iso-
tacticity catalyst recently. The propylene/butene-1 random
copolymers, both BOPP (biaxially orientated polypropylene)
lm and transparent container grades with less soluble content,
are extremely suitable for Chinese food packing since Chinese
food usually contains oil. The propylene/butene-1 random
copolymers are not only suitable for Chinese food packaging, but
also can benet Chinese PP manufacturers since butene-1 is even
cheaper than ethylene in China. The PP manufacturers in the
renery with lower cost monomer can also easily produce
propylene/butene-1 random copolymers. Therefore, propylene/
butene-1 random copolymers could be a kind of high perfor-
mance polypropylene with low cost in China.
BOPP lm is widely used for food packaging; therefore, BOPP
resin with low soluble content is required by the food packing
industry. However, high speed BOPP resin must contain more
than 4% soluble fraction according to traditional theory. Based
Liangshi Wang; Xiaofan Zhang; Meifang Guo; Luqiang Yu; Dongbing Liu; Yiqun Liu and Wenbo Song
1612 | Polym. Chem., 2011, 2, 16111623 This journal is The Royal Society of Chemistry 2011
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on a fundamental research breakthrough in the so called 973
program,
6
SINOPEC has developed a technology to produce
high speed BOPP resin with soluble fraction of less than 2%,
which is extremely suitable for food packaging.
1.4 Low VOC impact PP
Impact PP grades with high melt ow index (MFI) are usually
produced via a controlled-rheology process, where PP with low
MFI is produced in a reactor rst and then peroxide is used to
reduce PPs molecular weight. This process inevitably produces
a lot of VOCs in the nal PP resin. VOCs can give plastic
products unpleasant smell like that in new cars. In order to
reduce VOCs, the key point is to produce high MFI impact PP in
the reactor directly with the help of external-donors. Among the
processes developed is SINOPECs unique asymmetric external
donor (ASD) process,
7
which will be introduced in section 3.2 of
this review.
1.5 Phthalate free PP
Phthalate has been found to be harmful to health, e.g. reducing
male semen; therefore, materials containing phthalate have been
restricted around the world. Unfortunately, PP catalysis
commonly uses phthalate as an internal donor. The use of
phthalate containing PP is likely to be prohibited in the near
future, especially in food and toy industries.
Several phthalate free PP catalysts have been commercialized
in recent years and make phthalate free PP available, which will
be reviewed in section 2.2 hereunder. For example, Lyondellba-
sell and SINOPEC can produce various PP grades without
phthalate based on their phthalate free PP catalysts.
1.6 Reactor-made high performance PP
A large amount of modied PP or PP compounds are used in
automobile industry and household appliances because virgin PP
resins could not meet the requirements of these industries in the
past. Secondary processing apparently means more energy use
and more pollution; therefore, it is necessary to develop high
performance PP resins directly from the reactor to replace
modied PP. In recent years, reactor-made high melt strength PP
and high performance impact PP have been developed and made
a market success.
High melt strength PP (HMSPP) has been used in PP foaming,
thermoforming and many other applications. However, HMSPP
manufacturing is a costly process. The rst commercial HMSPP
was produced by irradiation process and then followed by
reactive extrusion process. In recent years, reactor-made HMSPP
is available by different technologies, such as Dows metallocene
catalyst technology, Lyondellbasells Spherizone process and
SINOPECs ASD process. With those new technologies,
HMSPP will replace more other materials. For example, foamed
PP made of HMSPP will replace more and more foamed poly-
styrene.
The automobile industry consumes a lot of PP compounds,
such as in bumpers. Now the PP manufacturers can supply
reactor-made PP resin that can satisfy the automobile industrys
requirement for bumpers. It only needs a newmould to overcome
the shrinkage difference between PP resins and PP compounds.
SINOPEC has developed a special impact PP resin for car
bumpers and successfully replaced some PP compounds in
China.
1.7 Functional polyolen with lower cost
Functional polyolens account for only a small market share,
one reason for this is due to their high cost. For example, anti-
bacterial polyolen can benet human health, but it is not very
popular in the market because of the expensive anti-bacterial
additives used. In order to reduce the cost, SINOPEC has
developed a compound additive technology platform for high
efciency additives including a-PP nucleating agent, b-PP
nucleating agent, LLDPE nucleating agent, laser marking
pigment, anti-bacterial agent, etc. With the help of this tech-
nology, some high performance polyolens with lower cost have
been commercialized, which will be introduced in section 4 of this
review.
2. Catalyst development
The history of polyolen is actually the history of catalyst
development. The catalyst, from ZieglerNatta catalyst and
Phillips catalyst to single-side catalyst, allows us to control the
polyolen purity, isotacticity and isotacticity distribution. It was
the breakthroughs in catalyst technology that eliminated the
process for the removal of the atactic fraction and catalyst resi-
dues to make the polymerization process simpler and cleaner. It
was also the breakthroughs in catalyst technology that expanded
the product properties envelope of polyolens to make poly-
olens market share increase continuously.
2.1 PE catalysts
After LDPE, a non-catalyzed polyolen developed by the
Imperial Chemical Industries (ICI) in the 1930s, HDPE, LLDPE
and PP became major plastics with the development of Ziegler
Natta catalysts
8
and chromium catalysts
9
in the 1950s. After
more than 50 years of development, now there are four types of
PE catalysts, ZN catalysts, chrome catalysts, metallocene
single-site catalysts and non-metallocene single site catalysts.
2.1.1 ZieglerNatta catalysts. Modern PE industry was
started from a breakthrough of high activity catalyst made by
Mitsui Chemical and Montecatini in 1968. This famous catalyst
was TiCl
4
supported on MgCl
2
carrier and its activities were
more than 100 times higher than traditional TiCl
3
catalysts.
10
This high activity catalyst not only simplied the polyethylene
polymerization process by deleting the de-ash process, but also
improved the performance of the polyethylene resin. Afterwards,
ZN catalyst development was focused on catalyst performance
improvement and catalyst suitability for the polymerization
process, such as modifying the morphology of the catalyst
particle to narrow particle size distribution and achieve spherical
morphology, increasing the sensitivity of H
2
response, decreasing
the ne content of PE particles, increasing bulk density of PE
powder, etc.
An emulsion process for ZN catalyst preparation was
developed by Borealis recently. The process was originally
developed for PP catalysis and then found to be also suitable for
This journal is The Royal Society of Chemistry 2011 Polym. Chem., 2011, 2, 16111623 | 1613
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PE catalysis. The catalyst particles have an extremely low surface
area, perfect spherical particle shape and a narrow particle size
distribution. The polymer particles produced with this catalyst
are compact and perfectly spherical with a narrow particle size
distribution, reduced porosity, high bulk density and intra-
particle homogeneity.
11
This catalyst also leads to a polymer with
advanced properties, such as a low level of nes etc.
12,13
N-series PP catalyst (BASF Lynx 1000 series based on the
same patent technology) developed by SINOPECBRICI delivers
PP with higher isotacticity and better stability. Recently SINO-
PECBRICI extended the N-catalyst technology to PE catalyst as
BCE and BCS catalysts for slurry and gas-phase processes. The
BCE catalyst is a new generation high activity PE catalyst for
slurry process.
1416
The catalyst can be applied to CX, Hostalen,
Innovene and Phillips loop processes to produce HDPE, espe-
cially high added value grade, such as PE-100+ pipe grade and
PE powder for CPE (chloride polyethylene) grades. The BCE
catalyst has narrower particle size distribution; therefore, PE
resin produced with the BCE catalyst has a lower ne content
and higher polymer bulk density. The BCE catalyst also has
better copolymerization ability, which can decrease the content
of soluble low molecular weight PE. The PE production process
with BCE catalyst consumes less energy, less steam and has
a long operation cycle with easy and stable operation. The BCS
catalyst is a slurry injection catalyst for gas phase process to
produce LLDPE resin. The BCS catalyst has such advantages as
high activity, excellent co-polymerization, good owability, good
particle size distribution of both catalyst and PE, and low ne
content.
17
2.1.2 Chromium catalysts. The Cr/SiO
2
catalysts, also called
Phillips catalysts, are still important catalysts for HDPE with
broad molecular distribution. The Phillips catalysts have
attracted a great deal of academic and industrial interest.
However, the structures of active sites remain controversial until
now.
18,19
Even recently McDaniel from Chevron-Phillips
Chemical Co. still published papers on the activation of this
catalyst.
2023
The PE industry always has the dream of producing
HDPE with Cr catalyst in reduced condensing mode in a gas
phase process; therefore, many researchers have been continu-
ously striving to increase the activity of Cr catalyst in gas phase
polymerization process.
2.1.3 Metallocene catalysts. In 1980, Kaminsky reported that
zirconocene/MAO (methylaluminoxane) could be used for olen
polymerization with high activity at the IUPAC Polymer
Congress in Firenze.
24,25
Afterwards, metallocene catalysts, as
single site catalysts, became great focuses of industrial and
academic research. The catalyst supporting technology is always
one of main hot research elds because only the supported
metallocene catalysts can be directly used in the current gas phase
or slurry processes. Several papers have reviewed the advance on
supporting metallocene catalysts in detail.
26,27
From the industrial point of view, increasing the supported
catalysts activity and reducing catalyst cost are still the most
important issues. Recently Albemarle developed a technology,
ActivCat technology that can increase the productivity of
conventional MAO/silica metallocene catalysts by 200%.
28,29
SINOPEC BRICI developed a MgCl
2
modied silica carrier for
metallocene catalyst that can increase activity of a supported
catalyst by more than 50% compared with traditional silica
supported catalysts.
30
Borealis developed an emulsion-based single-site catalyst
preparation process as described in Fig. 1.
31
This process enables
catalyst particles to have an inherently perfect spherical shape
and unique intra and inter-particle homogeneity. The catalyst
has higher catalyst activities and its morphology is shown in
Fig. 2. The catalyst particles are very compact and have a low
surface area.
Single reactor bimodal HDPE technology is another PE
catalyst hot research eld. Univation has developed the
PRODIGY Catalyst for bimodal HDPE in a single gas phase
reactor.
32
The PRODIGY Bimodal Catalyst system has two
single site catalysts, a metallocene catalyst and a post-metal-
locene catalyst for HMW and LMW components. Another
representative single site catalyst, as reviewed in 1998 by
McKnight and in 2003 by Gibson, is an ansa-cyclopentadienyl-
amido group IV catalyst called constrained geometry catalyst
(CGC).
33
In the 1990s, Dow Chemical Company commercialized
the CGC technology to produce polyolen plastomers and
elastomers with long-chain branches in a solution process.
2.1.4 Non-metallocene single-site catalysts. Brookhart devel-
oped the Ni, Pd, diimine catalyst system for olen polymeriza-
tion in 1995,
34
which was also called the late transition metal
catalyst. Afterwards, many other non-metallocene single site
catalysts were developed, such as Grubbs catalysts,
35
FeBis(imino)pyridine catalysts,
36
FI catalysts
37
etc. Gibson has
reviewed the non-metallocene single-site catalyst in detail.
33
So
far only a few non-metallocene single-site catalysts were
commercialized.
The pyridyl amine-base catalyst was developed by Dow
Chemical Company in conjunction with Symyx high throughput
technologies in 2004. The catalyst as shown in Fig. 3 is a non-
metallocene single site catalyst. It allows copolymerization of
Fig. 1 The preparation process for emulsion-based single-site catalyst.
Fig. 2 SEM image of the single site catalyst prepared by the emulsion-
based process.
1614 | Polym. Chem., 2011, 2, 16111623 This journal is The Royal Society of Chemistry 2011
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propylene with various olen comonomers over a broad range of
compositions in an isotactic fashion and with high molecular
weight. Dow commercialized the propylene/ethylene copolymer
under the trademark VERSIFY. The VERSIFY plastomers and
elastomers have a very narrow molecular weight distribution,
a broad and unique composition distribution and unique regio-
errors.
3
Chain shuttling catalyst technology is another of Dows
innovations on single site catalysts. Chain shuttling is dened as
the passing of a growing polymer chain between catalyst sites,
such that portions of a single polymer molecule are synthesized
by at least two different catalysts. The chain shuttling agent
(CSA) is a component that facilitates this transfer, such as
a metal alkyl complex. The chain shuttling mechanism can be
described in Fig. 4.
5
Cat1 (solid circles) and Cat2 (solid triangles) represent cata-
lysts with high and lowmonomer selectivity respectively, whereas
the CSA (solid squares) facilitates the chain shuttling reaction.
Cat1 produces a segment of hard polymer with low comonomer
content. Shuttling occurs when this segment is exchanged with
the CSA bearing a soft copolymer with higher comonomer
content. Further chain growth at Cat1 then extends the soft
copolymer chain with a hard segment, thus giving a block
copolymer. Pyridyl amine-based catalyst is used as Cat2 to
produce the segment of soft polymer and salicylaldiminato-type
catalyst (known as FI catalyst) is used as Cat 1 for the segment of
hard polymer.
In 2006, Dow announced ethyleneoctene INFUSE olen
block copolymers (OBCs), which are produced using the chain
shuttling catalyst technology. This technology employs two
catalysts, one forming high-density PEwith higher melting points
and the second forming an elastomer with high incorporation of
octene in the ethylene chain. Achain shuttling agent, diethyl zinc,
forces anexchange of catalysts as the polymer chaingrows leading
to block polymers that combine the attributes of high-density PE
and the olen elastomer. Compared to ethyleneoctene random
copolymers made by metallocene catalysts, the block architecture
of OBCs imparts a higher crystallization rate and higher melting
temperature while maintaining a lower glass transition tempera-
ture and a more highly order crystalline morphology. Because of
these structural differences, the physical and mechanical proper-
ties of OBCs are different from random copolymers, resulting in
better performance in many applications.
2.2 PP catalysts
Since the rst isotactic PP formed with TiCl
3
-AlR
3
catalyst was
developed in 1954,
38
PP catalysts have been the main research
focus for both the PP industry and academia. There are three
major series of PP catalyst systems now: traditional Ziegler
Natta catalysts, metallocene catalysts and non-metallocene
single-site catalysts.
2.2.1 ZieglerNatta catalysts. The traditional ZieglerNatta
catalyst is still the most widely used catalyst system in the poly-
propylene industry. In the development history of the Ziegler
Natta catalyst there are ve generations of catalysts and the
electron donors have played an important role.
39
As early as the
rst generation of the catalyst, it was found that addition of
a third component would make a huge impact on the olen
polymerization behavior and polymer properties. This third
component was actually an electron donor, also known as the
Lewis base. The Lewis base that is added in the preparation of
solid catalyst is called an internal donor, while the Lewis base
added in the olen polymerization process is called an external
donor. The nature of the electron donor has signicant inuence
on active sites and catalyst properties. Therefore, PP catalyst
research is always focused on more efcient routes for catalyst
preparation and more efcient combinations of electron
donors.
40
2.2.1.1 Internal donors. In the early 1980s, a MgCl
2
sup-
ported catalyst systemwith a new internal donor, alkylphthalate,
was developed. This new catalyst could afford much higher
catalytic activity and isotacticity, so that de-ashing and removal
of the atactic polymer could be avoided.
41
This catalyst is called
the fourth-generation ZN catalyst, so far it is still widely used in
the polypropylene industry. Since then, many further studies on
electron donors have been done. Many internal donors have been
developed, such as 1,3-dione, isocyanate, 1,3-diether, malonic
ester, succinate, 1,3-diol ester, glutaric acid ester, diamine, 1,4-
diol, 1,5-diol ester, phthalate esters, cycloalkyl esters and the use
of a variety of binary electron donor complex etc. The catalytic
properties differ a lot when different kinds of compound are used
as the internal donor. At present, the catalysts using 1,3-diether,
succinate or 1,3-diol ester as the internal donor have been
commercialized or are in the stage of application promotion.
42
The catalysts with these three types of internal donors are all
phthalate free and so are the polypropylenes made with these
catalysts.
1 1,3-Diethers as internal donors. In 1989, a PP catalyst with
1,3-diether as the internal donor was developed by the Himont
Fig. 3 Pyridyl amine-based catalysts.
Fig. 4 Depiction of the likely chain shuttling mechanism in a single
reactor, dual-catalyst approach.
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company. This new internal donor provided a PP catalyst with
extremely high activity and isotacticity without the need for any
external donor, which breaks the restrictions of the last two
generations of catalyst that the PP catalyst must contain both
internal and external donors.
43
It could be considered as the fth
generation of PP ZN catalyst. Compared with the conventional
catalyst, the diether catalyst has higher activity, higher hydrogen
sensitivity, and narrower molecular weight distribution. More-
over, the obtained polymer exhibits high isotacticity and low
oligomer content. Diether catalyst has been successfully applied
to Montell Spheripol process. At present, Basell has developed
a series of PP catalyst containing diether compound as the
internal donor. PPs obtained with these catalysts have narrow
molecular weight distribution, which is suitable for melt spinning
process. Due to the fact that the ZN catalyst with 1,3-diether as
an internal donor has excellent hydrogen sensitivity, it is also
suitable for the multi-reactor polymerization process, which can
broaden the molecular weight distribution of polypropylene in
existing operating conditions.
2 Succinates as the internal donors. Succinate as internal
donor was also developed by Basell. In 2003, Basell began to
commercialize their new ZN polypropylene catalysts with
succinate as internal electron donor.
43
The catalytic activity
increased and the polymer molecular weight distribution became
wider compared with the fourth generation catalyst using the
phthalate. The stiffness and processing performance of the
polypropylene resins made by this series of catalysts are greatly
improved. The new type of catalyst can be applied to most of the
PP production processes, including bulk, gas phase and slurry
processes.
3 1,3-Diol esters as the internal donors. In 2002, a new series
of PP catalysts were developed by SINOPEC BRICI with 1,3-
diol esters as the internal donors.
44,45
Such catalysts are charac-
terized by a high catalytic activity and better stereospecicity and
the obtained polymers have a wide molecular weight distribu-
tion. The hydrogen sensitivity can be varied by changing the type
and position of substituent of the 1,3-diol ester compound. In
addition, the PP performance has also been greatly enhanced.
The industrial application shows that the catalyst with 1,3-diol
esters has unique advantages and PP made with this catalyst can
be used in many applications.
2.2.1.2 External donors. The external donors also have great
inuence on polypropylene catalyst activity, hydrogen sensitivity
and stereospecicity. It is necessary that the internal and external
donors have proper match to each other.
46
At present, the most
commonly used catalyst in the PP industry is the fourth gener-
ation catalyst, containing phthalate as the internal electron
donor and the organic siloxane compound as external donor. In
the development of organic siloxane, many studies have shown
the great effect of the structures of alkyl and alkoxy on catalyst
performance.
4648
Proto and Sacchi found that the performance of organic
siloxane was affected by the alkoxy number, size, and groups
connected with the silicon atoms.
48,49
According to their study,
small alkoxy groups, such as methoxy and ethoxy were ideal for
suitable organic siloxane. For the non-alkoxy groups, the effect
of organic siloxane size on polypropylene isotacticity was in
sequence: methyl < butyl < isobutyl phenyl < isopropyl.
50
Currently the most commonly used external donors in PP
industry are methyl cyclohexyl dimethoxy silane (CHMDMS),
diisobutyl dimethoxy silane (DIBDMS), dicyclopentyl dime-
thoxy silane (DCPDMS) and diisopropyl dimethoxy silane
(DIPDMS). The effect on the stereospecicity was in the
sequence: DCPDMS > DIPDMS > CHMDMS > DIBDMS; the
effect on the hydrogen sensitivity was in sequence: DIBDMS >
CHMDMS > DIPDMS > DCPDMS.
47
Among the known
organic siloxanes, the catalyst using DCPDMS as an external
donor showed the highest stereospecicity, but the worst
hydrogen sensitivity. Therefore, when PP with a broad molecular
weight distribution is produced by using two external donors,
one must be xed on DCPDMS, another is usually an external
donor with high hydrogen response and moderate stereospeci-
city properties.
50,51
In recent years, scientists also have tried to develop new types
of external electron donors. A series of PP catalysts using amino-
silanes as external donors have attracted much attention.
52,53
The
catalyst with amino silane can broaden the polypropylene
molecular weight distribution without reducing its isotacticity
compared with the organic siloxane catalyst. It is also reported
that the polypropylene produced by the catalyst containing
a ring-amino-silane as external donor not only has a high crys-
tallinity, but also a wide molecular weight distribution.
54
When
diethyl amino-silane is used as external donor, the catalyst
exhibits high activity, high stereospecicity and good hydrogen
response.
55
Kemp developed an external donor, the calixarene, which is
a macrocyclic oligomer formed by condensation reaction of
phenol and formaldehyde.
56,57
Using calixarene as external
donor, the catalyst stereoregularity could be improved signi-
cantly while the catalytic activity changed slightly. When alkyl
group substituted calixarene was used as an external donor, the
PP isotacticity could be further enhanced while the catalytic
activity decreased. In addition, if calixarene substituted siloxane
was used as external donor, the catalyst stereoselectivity signi-
cantly increased while the activity changed little.
Himont also reported a kind of catalyst using 1,3-diether as an
external donor and phthalate as the internal donor. This catalyst
system has similar activity and hydrogen response to the catalyst
using 1,3-diether as an internal donor.
58
2.2.1.3 Catalyst preparation process. PP catalyst preparation
process can be simply divided into two categories: one is
preparing MgCl
2
support rst and then reacting the support with
TiCl
4
and the electron donor, such as Basells spherical catalyst;
the other is dissolving a magnesium compound rst and then co-
precipitating MgCl
2
with titanium in the presence of TiCl
4
, such
as the Mitsui Companys TK catalyst. Catalyst preparation
process is also important for catalyst performance. Although the
nal components of the solid catalyst made from different
processes are almost same, their microstructures can be quite
different, such as catalyst active center number and distribution,
so that the performance of catalysts can differ a lot.
In recent years, some new catalyst preparation processes have
been developed and among them the most noteworthy is the
emulsion process developed by the Borealis Company.
59
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Catalysts prepared by this method have good morphology and
narrow particle size distribution. PP produced by these catalysts
has narrow particle size distribution, low ne content, and high
bulk density. Although the catalysts prepared by this method
have a small surface area and low porosity, the catalytic activity
is still very high. This result introduces a newPP catalyst research
direction that is completely different from the traditional one. In
order to enhance catalyst activity, traditionally catalyst scientists
always concentrate on increasing the catalyst surface area and
porosity. Now the PP catalyst with small surface area and low
porosity can also have high activity.
2.2.2 Metallocene catalysts. Metallocene catalysts are
comprised of the central metal, the ligand containing cyclo-
pentadienyl (Cp) group and the activator (also known as co-
catalyst). Ligand structure plays a key role in catalyst perfor-
mance and only the ligand with appropriate substitution
combined with the most appropriate transition metal atoms can
form an efcient metallocene catalyst. Metallocene catalyst is
a kind of single-site catalyst. It offers precise control of not only
molecular weight, molecular weight distribution and crystal
structure but also to the comonomers position in the polymer
chain. The catalyst structure is very important. A large number
of studies show that polypropylene with different stereoregu-
larity including random, syndiotactic and isotactic and with
different copolymer composition can be made by using different
metallocene catalysts with different ligand structure.
In 1995, Coates and Waymouth
60
synthesized a non-bridged
metallocene catalyst (2-Ph-Ind)
2
ZrCl
2
with both meso and
racemic structures that can be converted to each other (Fig. 5). It
was found that the raceme mainly resulted in preparing isotactic
polypropylene, while the meso structure made random poly-
propylene segments and the segment length was determined by
the conversion rate between raceme and meso and monomer
insertion rate. By changing the polymerization conditions, PP
with various structures can be prepared. By changing the
substituents on the phenyl group of the ligand, the research team
developed a number of other metallocene PP catalysts with
similar properties.
61
Ewen and coworkers found that the C
S
-symmetrical metal-
locene catalyst, as shown in Fig. 6, can be used for producing
highly syndiotactic PP, which is a signicant breakthrough in the
development of syndiotactic polypropylene.
62
This nding not
only produced a new kind of plastic, but also provided proof for
the double active site polymerization mechanism of the metal-
locene catalyst.
The zirconocene catalysts rac-Et(Ind)
2
ZrCl
2
1
and the silicon-
bridged metallocene
2
(R
1
and R
2
are hydrogen) are the two most
thoroughly studied catalysts (Fig. 7). When R
1
is methyl
(complex 2), the molecular weight of polypropylene can be
signicantly increased. When R
2
is naphthyl, propylene poly-
merization activity of catalyst 2 is as high as 8.8 10
8
g PP/mol
M h, and polymer molecular weight is 920000, with a melting
point of 161

C, isotactic pentad ratio (mmmm) of 99.1%.
63
So
far 2-methyl-4-aryl-indenyl-based catalysts developed by the
Spaleck research team are the most successful metallocene
catalysts for producing isotactic polypropylene.
In recent years, one of the main research focuses on metal-
locene catalysts is new supports to further reduce the amount of
MAO and further improve the metallocene catalyst activity.
64
Grace has developed a support technology named IOLA, which
was prepared by spray drying a reactant of SiO
2
and clay.
65
IOLA is a micro spherical particle with very rough surface,
plenty of caves and pores inside. These micro particles were
ionized clay particles enabling the Lewis acid uniformly
dispersed throughout the particles and interacted easily in the
catalyst. In the pre-polymerization stage, IOLA acts as an acti-
vator for the catalyst, and in polymerization stage, it acts as
a support for the catalyst. Thus IOLA has dual functions as both
support and activator, eliminating the need for expensive MAO
or borane as a cocatalyst, dramatically reducing the production
cost of single-site catalysts.
Compared with metallocene polyethylene catalysts, the
development of metallocene polypropylene catalysts is relatively
slow. However, the metallocene polypropylene has shown its
advantages; therefore, the metallocene polypropylene catalysts
are expected to develop as good as metallocene polyethylene
catalysts in the future.
2.2.3. Non-metallocene single-site catalysts. This is another
kind of single site catalyst which does not contain cyclo-
pentadienyl, indenyl or a uorine-based ligand. The ligand in this
Fig. 5 The structure of rac- and meso-(2-Ph-Ind)
2
ZrCl
2
.
Fig. 6 C
S
-symmetrical metallocene catalysts.
Fig. 7 Ethyl- and dimethyl silicone-bridged metallocene catalysts.
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kind of catalyst is alkyl or aryl containing N, O, S, or P atoms.
Performance of the non-metallocene catalyst can reach or even
exceed the metallocene catalyst.
66
Some non-metallocene poly-
ethylene catalysts have been industrialized, while non-metal-
locene polypropylene catalysts are still in the laboratory stage.
The most representative three kinds of non-metallocene PP
catalysts are the diimine nickel/palladium catalysts, the pyridine
diimine iron/cobalt catalysts and the salicylaldiminato titanium/
zirconium catalysts.
In 1998, the Fujita group of the Mitsui Chemicals Company
developed a novel type of salicylaldiminato group IV transition
metal complexes, known as FI catalysts, which showed excellent
catalytic performance on olen polymerization.
67
Such catalysts
showed high polymerization activity for ethylene polymeriza-
tion. But for propylene polymerization, the stereoselectivity was
highly depended on the central metal and cocatalyst. With MAO
as the cocatalyst the salicylaldiminato zirconium catalyst is very
difcult to make high stereoselectivity polypropylene. However,
under certain polymerization conditions, the salicylaldehyde
titanium catalyst can prepare high regularity syndiotactic poly-
propylene.
68,69
It is also found that with iBu
3
Al/Ph
3
CB (C
6
F
5
)
4
as
cocatalyst, high molecular weight atactic polypropylene could be
prepared when using the salicylaldiminato titanium catalyst,
while moderate to high molecular weight isotactic polypropylene
can be prepared by zirconium or hafnium salicylaldiminato
catalyst with the same cocatalyst.
70,71
3. Polymerization process
3.1 PE process
In the past 10 years, the main PE processes almost remain
unchanged. However, some progress in modication of existing
processes has made PE process technology move forward. In
HDPE processes, the main advances were enlarging the device
capacity, using multi-reactors to manufacture multi-modal PE
products and simplifying the processes. For example, the
Chevron Phillips company had improved its loop process in
following aspects: (1) use larger scale reactor to realize the
economic benets; (2) reduce the number of devices; (3) improve
the equipments efciency and capacity; (4) simplify the instal-
lation, such as using aself-supporting reactor with fewer steel
structures; (5) improve the catalyst feed system; (6) improve
process control technology. The investment cost of the improved
devices was reduced by 50% compared to the old one designed in
1990. In order to produce bimodal and multi-modal HDPE
products smoothly, the improvement of Hostalen process was
mainly focused on the reactor cooling system, gas emission
system and de-waxing separation part.
In the LDPE process, the main progress lies in three areas:
improving product quality, increasing productivity and reducing
costs. For example, the capacity of single-tube CTR technology
has been increased to 400,000 tons per year. In high-pressure
autoclave LDPE eld, LyondellBasell has developed the Lupo-
tech A process that has a special monomer and initiator injection
system to control the reaction pressure and temperature distri-
bution, so as to obtain the higher conversion rate. This process
can be used to produce adhesives and sealants that contain up to
40% vinyl acetate.
The LLDPE process was mainly focused on further enlarging
capacity, bimodal LLDPE technologies, controlling comonomer
distribution and easy-processing metallocene LLDPE. To reduce
the cost of the production, the capacity of Unipol gas-phase
polyethylene reactor can reach 600,000 tons per year. Because of
the increase in the reactor diameter, heat transfer must be
strengthened in engineering, so are the materials transfer, the
predicting of reactor agglomeration and the technology of
reducing the transition product.
72
The Spherilene technology with
a dual-reactor recently took advantages of the Lupotech G tech-
nology to simplify the catalyst system and optimize exhaust gas
removal system. The Westlake Company developed a technology
to control comonomer distribution in polyethylene chain by
adding some special compound during polymerization, which can
improve the performance of LLDPE resin.
73
The Evolue process
now can use metallocene catalyst and a dual-reactor to produce
bimodal metallocene polyethylene. NOVA Chemicals have
adopted the Sclairtech dual-reactor and non-metallocene single-
site catalyst to produce high-performance LLDPE products.
74
3.2 PP process
Since the PP industry started in 1957, the advances in catalyst
technology and the demand for improving product performance
have always been the two main driving forces to promote the
development of propylene polymerization processes.
2
The typical
current PP processes are shown in Fig. 8.
Since the loop reactor has lots of advantages like high space-
time yield, full use of reactor volume, simple structure, less
investment in construction, excellent heat and mass transfer and
seldomfouling in the reactor etc., it is regarded as the best reactor
for propylene homo-polymerization. This leads the loop reactor
process to be the most important manufacturing process for
polypropylene now. Actually, the autoclave process has been
abandoned.
1,75,76
In order to improve the economics of plant operation, the scale
of polypropylene plants have become larger and larger, and the
largest production line is now over 450 kt/a. In order to meet the
requirement for high quality polypropylene products, APC
(advanced process control) technology has also been applied
universally.
77,78
Fig. 8 Some typical current polypropylene processes.
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Further improving polypropylene performance, such as poly-
mer exibility, rigidity and melt strength, is an important target
in the PP industry. Among current polypropylene processes,
some processes are designed for this purpose, such as the Cata-
lloy process developed by BASELL.
79,80
The Catalloy process is
based on reactor particle technology (RGT), in which broader
MWD, higher isotactic index, random copolymer with up to
15 wt% comonomer, multi-phase polyolen alloy containing
more than 70 wt% rubber can be produced. The most important
advantage of this copolymerization technology is that the low
modulus PP resins can be produced.
The commercial Spherizone process started in 2003 by the
Basell Company was the most important breakthrough in PP
production processes in the last 10 years.
81,82
The core technology
of the Spherizone process lies in the multi-zone circulating
reactor (MZCR), which contains two different regions, i.e. Riser
and Downcomer. Compared with the multi-reactor technology,
the residence time of the particles circulating around in MZCR is
much shorter than that in the multi-reactor, so that the particles
uniformity is improved signicantly.
Flexible control of catalyst properties is another way to ach-
ieve high performance polypropylene. It can be reached by
Asymmetric External Donor (ASD) technology developed by
SINOPEC Beijing Research Institute of Chemical Industry
(BRICI) in 2006.
7
The aim of ASD technology is to improve the
overall performance of broad molecular weight distribution PP.
Through regulating the amount and/or species of external donor
in different polymerization stages, the catalyst performance, such
as stereoregulating effect, hydrogen sensitivity and co-polymer-
ization behavior, can be controlled in different polymerization
stages by using ASDtechnology. The technology has been widely
applied in a series of PP products, such as the high performance
BOPP resin, PPH pipes, high melt strength polypropylene and
high melt index impact polypropylene with low VOC.
4. Additives
Additives are indispensable components for polyolen resins,
which can improve the resins processibility and other important
end-use properties. There are tens of different kinds of additives
used in polyolen resins, in which nucleating agent is one of the
most noteworthy additives. Some progress of PP nucleating
agent will be introduced in this section.
4.1 PP nucleating agent
Nucleating agent is an important additive for semi-crystalline
polyolen, especially for polypropylene. Some important phys-
ical and mechanical properties of PP resin can be greatly
improved when low levels (generally between about 0.01 and 0.5
wt%) of commercial high-performance nucleating agent are
added in the resin formula. The research concerning nucleating
agent is very active and there are hundreds of patents led in this
area. Some review articles or books have been published in the
last decade on various aspects of polymer nucleating agents.
8386
4.1.1 Ultra-ne or nano-sized melt insensitive nucleators.
Commercial PP nucleating agents can be divided into melt
sensitive and melt insensitive ones. Both types need adequate
dispersion prior to compounding, especially for melt insensitive
nucleators. The size of nucleating agent has substantial inuence
on the properties of PP. The larger the particle size, the lower the
nucleation efciency. Smaller nucleator particles usually generate
smaller spherulites, higher mechanical properties and better
transparency. Many researchers try to make nucleators with
smaller particle size in order to improve the dispersibility of
nucleators and their nucleating efciency.
Asahi Denka Corp.
87
reported using pulverization apparatus
to produce nely pulverized phosphoric acid aromatic ester
metal salt in a European patent application. By controlling
pulverization time, the average major-axis length of nucleator
can be adjusted between 0.15 microns and the resulting nucle-
ator has enhanced dispersibility. Their examples show that the
nucleator particle size can reach 0.3 microns after jet-milling
30 min and ball-milling for another 2.5 h. Particle size below
0.1 micron is not preferred due to higher pulverization cost and
lowering of uidity.
Xinzhong et al.
88
disclose a method for producing ultrane
organic phosphate nucleating agent. Said method includes the
following steps: dissolving organic phosphate nucleating agent in
organic solvent, adding surfactant, adding water to the above-
mentioned solution under stirring, then collecting the described
ultrane organic phosphate nucleating agent from the reaction
product. Its average particle size is less than 0.3 micrometres.
Libster et al.
89,90
disclosed a novel dispersion method to
improve the nucleation efciency of a water soluble nucleator,
bicycloheptane dicarboxylate salt, commercially known as HPN-
68 from Milliken. Their concept is based on using microemulsion
technology as a transport vehicle. The nucleating agent must be
dispersed in a microemulsion to decrease its size from micro to
nanoscale, which was then introduced to the target PP using
a mixer. By the end of the melt mixing, when the water phase had
evaporated, only the nucleator and the surfactant remained in
the matrix. SEM results showed a four-fold decrease in the PP
spherulite size due to the improved dispersion of HPN-68 within
the matrix via microemulsion compared to conventional nucle-
ator incorporation. DSC results show that only 50 ppm HPN-68
is sufcient to achieve the highest T
C
, similar to the one obtained
by adding 300 ppm dispersed nucleator powder, i.e. 20% nucle-
ating agent is required to achieve the same nucleating effect.
4.1.2 In situ nucleating technologies. The current nucleating
technologies are mostly post-reactor technologies, i.e. nucleating
agents are incorporated into polyolen resin after the resin
powder has been produced from the reactor. The dispersion of
nucleating agent during the melt pelletizing process is critical to
ensure good nucleating effect and resin properties for these
technologies. Another category of nucleating technology can be
described as in situ technology, i.e., nucleating agent is combined
with polymerization catalyst or can be transformed after catal-
ysis process. This kind of in situ technology can theoretically
make very uniform dispersion of nucleating agent in resin
matrices. However the polymerization activity of ZieglerNatta
catalysts is susceptible to various functionalities related to the
nucleating agent. Most research concerning in situ nucleating
technology is accordingly focused on single-site catalysts, which
can still function well under environment of multiple functional
groups.
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Xinzhong et al.
91
disclosed a non-metallocene compound for
catalyzing and nucleating polyolen. This non-metallocene
compound (as shown in Fig. 9) can be supported on magnesium
halide to catalyze olen polymerization. After catalysis, the
compound is deactivated to become the nucleating agent for
crystallizing polyolen to raise the crystallization performance,
mechanical performance and optical performance of polyolen
greatly.
Yi et al.
92
developed a method of exploiting a nucleation agent
as support for metallocene catalyst. The metallocene compound
can be well supported on 1,3,2,4-dimethyl benzylidene sorbitol
(DMBS), a sorbitol based nucleating agent. Propylene poly-
merization with the supported catalyst resulted in i-PP polymers
with granular morphology. The role of a catalyst support ensures
Fig. 9 The chemical structure of non-metallocene catalysts.
Fig. 10 Comparison between nucleating effect of NA-11 and NA-11/ENP compound in different PP matrices. (a) and (b) in high isotactic PP matrix; (c)
and (d) in regular homo-PP matrix; (e) and (h) in heco-PP matrix; (g) and (f) in raco-PP matrix.
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a good dispersion of the nucleation agent in the formed i-PP
matrix. The i-PP/DMBS composition exhibits a much higher
crystallization temperature (T
C
) than the neat i-PP (129.5 vs.
113.3

C), as well as much ner spherulites, a typical represen-
tation of crystallization with the assistance of nucleation agent.
4.2 Improving efciency of polyolen additives with
elastomeric nanoparticles
Apart from a few polyolen additives such as antioxidants etc.,
which can be molten and well mixed with the resin matrix via
melt compounding with polyolens, most additives need to be
well dispersed in polyolen matrix so as to function well at low
addition levels. Some powerful additives are usually expensive
and the improvement of their efciency means the reduction of
additive loading and reduction of polyolen resin cost, which is
thus very attractive for resin producers and converters.
Rigid nanoparticles such as nanosilica, layered silicate etc. are
well known and have been used as polymer llers for many years.
The elastomeric nanoparticles (ENPs) mentioned here are ex-
ible powder made from rubber latex through Narpow tech-
nology invented by SINOPEC BRICI a decade ago. These ENPs
are used as toughening agent for thermoplastic
9396
and ther-
mosetting resins.
9799
The Narpowtechnology uses rubber latex
and irradiation sensitive as raw material and fully vulcanizes the
latex particles through irradiation and nally spray-dries the
vulcanized latex to obtain ENP products.
100,101
It can be inferred
fromthis manufacturing process that the surface part of ENP has
a higher cross-linking degree than the interior due to a higher
concentration of irradiation sensitivity near the surface part as
well as more reactions with excited molecules and ions in water
produced by the irradiation. Such a unique structure assures that
ENPs maintain good elastic properties and at the same time the
agglomerates of ENPs can still be easily broken apart and well
dispersed in a plastic matrix.
It has been found in recent years that ENP can signicantly
improve the efciency of some plastic additives, which means
a similar or better performance can be achieved at lower loading
of additive when ENPs are compounded with the corresponding
additive. The compound nucleating agent introduced in this
review is one of the examples that ENPs can improve the
efciency of PP additives.
102
The compound nucleating agents can be obtained by mixing
commercial nucleating agents, such as sodium 2,2
0
-methylene-
bis-(4, 6-di-t-butylphenylene) phosphate (NA-11) and styrene-
butadiene rubber ENPs. The nucleating effects of pure NA-11
and the compound were compared in different PP matrices as
shown in Fig. 10. The crystallization temperature, exural
modulus and heat distortion temperature curves all showthat the
compound nucleating agent has better properties even at lower
loading. Typically ca. 25% of NA-11 concentration in the
compound nucleating agent can achieve the same or even better
nucleating effect as compared to pure NA-11. This technology
has been successfully applied to some high impact heco-PP
grades and high crystalline homo-PP grades in SINOPEC in
recent years. And more than 100,000 tons of high performance
PPs with lower cost have been produced by using this compound
nucleating agent in recent years.
Even though the direct observation of nucleator in PP matrix
is difcult due to its low concentration, some indirect experi-
mental results as shown in the PLM micrographs (Fig. 11)
indicate that the crystal size is smaller and the nuclei density is
higher in PP sample nucleated with compound nucleator. These
results can be preliminarily used as evidence to prove that ENPs
can promote the dispersion of nucleator in PP matrix and
enhance the nucleating efciency accordingly.
5. Polyolen development in china
China is now a major polyolen consumer and producer in the
world. Mainland China consumed about 28 million tons and
produced about 16 million tons of polyolens in 2009. Chinas
polyolen industry uses monomers from 3 sources, ethylene
plant, renery and MTO/MTP plant. Based on coal, the MTO/
MTP-polyolen industry has grown very fast in China recently.
There are 1.52 million tons/a polyolen capacity based on MTO/
MTP at present and more capacity is still in construction in
China. It is difcult for polyolen manufacturers to avoid erce
competition in China because polyolen capacity increases much
faster than consumption does in China and nearby countries
recently. To meet the challenge, major polyolen producers such
as SINOPEC have targeted development and production of both
sustainable products with environmental and safety benets and
speciality high performance polyolen.
The polyolen is so important in China that even the funda-
mental research of polyolen has been supported by 973
program for 10 years from 1999 to 2010. 973 program, the
Fig. 11 PLM micrographs of homo-PP modied by 0.4& NA-11 (a)
pure NA-11 (b) NA-11/ENP compound.
This journal is The Royal Society of Chemistry 2011 Polym. Chem., 2011, 2, 16111623 | 1621
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National Basic Research Program, is Chinas on-going national
keystone basic research program organized by the Ministry of
Science and Technology. The program was granted more than 10
million USD to support the scientists from universities, Chinese
Academy of Sciences and SINOPEC working together on basic
polymer science, such as basic polymer science in random poly-
olen copolymer and impact PP. The 973 program on poly-
olen has had great achievements and some of them have been
introduced in this review.
The polymer scientists in China, including university profes-
sors, researchers from Chinese Academy of Sciences and
industry, are still carrying on studies on the basic science and
technology of polyolens, such as co-monomer distribution on
different macromolecules, anti-static, printability, and special
requirements for washing machine to prevent the barrel from
going mouldy. The polyolen industry in China will continue to
develop in the future.
6. Abbreviations
LDPE low density polyethylene
HDPE high density polyethylene
LLDPE linear low density polyethylene
PP polypropylene
VOC volatile organic compounds
PE polyethylene
PE-RT polyethylene of raised temperature resistance
PVC poly(vinyl chloride)
SBS poly(styrene-b-butadiene-b-styrene)
SIS poly(styrene-b-isoprene-b-styrene)
SEBS poly(styrene-b-ethylene butylene-b-styrene)
TPVs thermoplastic vulcanizates
OBCs olen block copolymers
FDA Food and Drug Administration
EU European Union
POE polyolen elastomer
POP polyolen plastomer
APAO amorphous poly-alpha-olen
BOPP biaxially orientated polypropylene
MFI melt ow index
ASD asymmetric external donor
HMSPP high melt strength polypropylene
ICI Imperial Chemical Industries
Z-N ZieglerNatta
CPE chloride polyethylene
MAO methylaluminoxane
IUPAC International Union of Pure and Applied
Chemistry
HMW high molecular weight
LMW low molecular weight
CGC constrained geometry catalyst
FI salicylaldiminato-type catalyst
CSA chain shuttling agent
CHMDMS methyl cyclohexyl dimethoxy silane
DIBDMS diisobutyl dimethoxy silane
DCPDMS dicyclopentyl dimethoxy silane
DIPDMS diisopropyl dimethoxy silane
Cp cyclopentadienyl
APC advanced process control
RGT reactor particle technology
MWD molecular weight distribution
MZCR multi-zone circulating reactor
SEM scanning electron microscope
DMBS 1,3,2,4-dimethyl benzylidene sorbitol
ENP elastomeric nano particles
USD United States dollar
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