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HIGHLIGHT

The Discovery and Progress of MgCl2-Supported TiCl4


Catalysts
NORIO KASHIWA
R & D Center, Mitsui Chemicals, Incorporation, 580-32 Nagaura, Sodegaura,
Chiba 299-0265, Japan
Received 20 August 2003; accepted 22 August 2003

ABSTRACT: Polyolefins represented by polyethylene (PE) and


polypropylene (PP) are indispensable materials in our daily lives.
TiCl3 catalysts, established by
Ziegler and Natta in the 1950s, led
to the births of the polyolefin industries. However, the activities
and stereospecificities of the TiCl3
catalysts were so low that steps for
removing catalyst residues and low
stereoregular PP were needed in
the production of PE and PP. Our
discovery of MgCl2-supported
TiCl4 catalysts led to more than
100 times higher activities and extremely high stereospecificities,

which enabled us to dispense with


the steps for the removals, meaning the process innovation. Furthermore, they narrowed the molecular weight and composition
distributions of PE and PP, enabling us to control the polymer
structures precisely and create
such new products as very low
density PE or heat-sealable film at
low temperature. The typical example of the product innovations
by the combination of the high stereospecificity and the narrowed
composition distribution is highperformance impact copolymer
used for an automobile bumper

that used to be made of metal.


These process and product innovations established these polyolefin
industries. The latest MgCl2-supported TiCl4 catalyst is very close
to perfect control of isotactic PP
structure and is expected to bring
about further innovations. 2003
Wiley Periodicals, Inc. J Polym Sci Part A:
Polym Chem 42: 1 8, 2004

Keywords: MgCl 2 -supported


TiCl4 catalysts; polyolefins; stereospecific polymers; copolymerization; polyethylene (PE); poly(propylene) (PP)

Dr. Norio Kashiwa is a senior research fellow of Mitsui Chemicals, Inc.,


who is offering that position only to him. He graduated from Osaka
University (Japan) in 1964 and received his masters degree in engineering
from the same university in 1966. Then, he joined Mitsui Petrochemical
Industries in the same year. He discovered MgCl2-supported TiCl4 catalysts in 1968. It brought about process and product innovations in
polyolefin industries, and now those catalysts constitute the majority of
global polyolefin production. Since then, he has been in the front line of
olefin polymerization catalyst research including not only MgCl2-sup-

NORIO KASHIWA
Correspondence to: N. Kashiwa (E-mail: norio.kashiwa@
mitsui-chem.co.jp)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 42, 1 8 (2004)
2003 Wiley Periodicals, Inc.

J. POLYM. SCI. PART A: POLYM. CHEM.: VOL. 42 (2004)

ported TiCl4 catalysts but also single-site catalysts such as metallocene


and post-metallocene catalysts. He received his Ph.D. from Kyoto University in 1985. He became board director of Mitsui Petrochemical
Industries in 1993, managing director of that company in 1995, and
managing director of Mitsui Chemicals in 1997 before his present appointment. He is also former vise president of The Chemical Society of
Japan. His achievement in MgCl2-supported TiCl4 catalysts research led
him to The Chemical Society of Japan Award for Technical Development
in 1985 and The Association of Chemical Engineers (Japan) Award in
1986, and his achievement in metallocene catalysts research led him to
receive The Chemical Society of Japan Award for Technical Development in 2003. In 2003, he was awarded a gold medal by the Minister of
Education, Culture, Science and Technology of Japan.

INTRODUCTION
Polyolefins represented by polyethylene (PE) and
polypropylene (PP) are indispensable materials with certain social impact in countless, beneficial ways. The
polyolefin industries began in the 1950s because of discoveries of TiCl3 catalysts by Ziegler and Natta.1 4
However, the catalyst activities and stereospecificities
were so low that enormous effort was invested to increase them. In 1968, our discovery of an MgCl2-supported TiCl4 catalyst5 brought about a breakthrough and
led to innovative improvement of the properties of the
polyolefins and a drastic cut of the production costs of
them. The achievements by MgCl2-supported TiCl4 catalysts boosted up the growth of the polyolefin industries
by replacing not only TiCl3-catalyzed products but also
the other materials such as paper, wood, metal, or engineering plastics. Therefore, the worldwide production
volume of polyolefins has grown to more than 80 million
tons per year until now and is predicted to rise continuously at a high rate, allowing us to use them in our daily
lives in such applications as packing materials, containers, films, sheets, pipes, automobile parts, electric and
electronic parts, medical and sanitary products, toys,
kitchen helpers, construction materials, and agricultural
materials. Figure 1 shows these catalysts for PE and PP
commercial productions and an estimate of their global
proportion in 2001. MgCl2-supported TiCl4 catalysts
constitute the majority because they have brought about
the process and product innovations and established the
polyolefin industry. I introduce how we discovered them
and what they have delivered.

THE DISCOVERY
When I joined Mitsui Petrochemical Industries, Ltd.
(now Mitsui Chemicals, Inc.) in 1966, it had passed

around 10 years since the commercialization of the TiCl3


catalysts. The discoveries by Ziegler and Natta were the
origins of coordination polymerization of olefins with
transition-metal catalyst systems. They created linear
polyolefins such as high-density PE (HDPE), linear lowdensity PE (LLDPE), and PP, whereas high-pressure
radical polymerization had given hyperbranched lowdensity PE (LDPE). Thus, all of the now common polyolefins led to births in the industries by their discoveries.
However, the activities of the TiCl3 catalysts were so
low that a step for removing catalyst residues (de-ashing)
was needed in the commercial production process for the
polyolefins. Without the de-ashing, the polyolefins
would have been colored and would have caused rust
that molds machines. Besides, in the case of PP production their stereospecificities were so low that a considerable amount of low stereoregular PP (so-called ata-PP;
soluble in boiling haptane) was contained in the resulting
PP. Therefore, a step for removing ata-PP was also
needed in the commercial production process for PP
because ata-PP diminished the PP properties. We hoped
to enhance the activity and stereospecificity to an acceptable level to dispense with the extra facilities and energy
for removing the undesirable components. For it, more
than 100 times higher activity than those of the TiCl3
catalysts and more than 96% of ratio of boiling heptane
insoluble part to the whole PP (I.I.) had to be accomplished, whereas the TiCl3 catalysts gave only about 90%
of I.I.
The favored method for increasing the activity at that
time was to support the active species on the surface of
inorganic materials with chemical reactions. A reaction
of TiCl4 with the hydroxyl group on such a support as
silica, alumina, or Mg(OH)Cl was regarded as a good
tool. It was said6 that the concentration of active sites of
the TiCl3 catalysts was less than 0.1%, namely, it was
agreeable that the internal TiCl3 should be replaced by an
inorganic support. However, the activities of these catalysts were at most five times as high as those of the TiCl3

HIGHLIGHT

Figure 1. Catalysts for global PE and PP production.

catalysts, and it seemed to reach its ceiling. I did not have


an idea to make them more than 100 times higher activity
by extending that concept.
My new concept to enhance the activity was gilding,
where a similar crystal to TiCl3 is plated with Ti active
species with liquid TiCl4. As a result of my investigation
based on this idea, MgCl2 should have been the best
ground crystal belonging to the same hexagonal group as
TiCl3, and Mg2 and Ti4 have similar ionic radii, 0.68
and 0.65 , respectively. However, it was very difficult
to plate MgCl2 with TiCl4 because MgCl2 has high
crystallinity with low specific surface area and no reactive groups with TiCl4. I decided to go upstream and start
with crystallizing MgCl2. I destroyed MgCl2 crystal by
adding such compound as n-butanol or methyl acetate
and confirmed recrystallization of MgCl2 by removing
the added compound. Then, I found that TiCl4 was
incorporated onto the MgCl2 surface in the recrystallization when I used an excess amount of TiCl4 for removing
the added compound. This is the moment when the
MgCl2-supported TiCl4 catalyst was discovered.
Table 1 lists specific surface areas of MgCl2, n-butanol-added MgCl2, and the product of the reaction with an
excess amount of TiCl4. The specific surface area increased drastically through the reaction because the
growth of MgCl2 crystal in the recrystallization was
terminated by the incorporated TiCl4, leading to assemblies of fine MgCl2 crystallites that could be identified by

the characteristic broad peaks in X-ray diffraction analysis as shown in Figure 2. Furthermore, the incorporated
TiCl4 would be located on the surface of MgCl2 as
shown in Figure 3,7 leading to effective formation of the
active species. Then, Et3Al was needed for the best
performance of this catalyst instead of Et2AlCl in the use
of TiCl3 catalyst. Such a difference in selecting the
cocatalyst would indicate not only the influences of the
different affinity unit of the Ti compound but also the
effects of MgCl2 on the active site. Thus, I found the
MgCl2-supported TiCl4 catalysts demonstrating more
than 100 times higher activities than the TiCl3 catalysts.
We applied a patent about the MgCl2-supported TiCl4
catalysts for the first time (according our best knowledge) on August 1 in 1968.5 Interestingly, Montecatini
who developed MgCl2-supported TiCl4 catalysts inde-

Table 1. Changes of Specific Surface Area by the Reaction


of MgCl2-2(n-Butanol) with TiCl4 at a Ratio of 1:12

Solid
MgCl2
MgCl2-2(n-butanol)
Product of the reaction between
MgCl2-2(n-butanol) and 12 equiv TiCl4

Specific Surface
Area (m2/g)
0.75
1.49
292

J. POLYM. SCI. PART A: POLYM. CHEM.: VOL. 42 (2004)

content of a comonomer and a low-molecular-weight


part possessing a low content of the comonomer (as
illustrated in Fig. 4) to accomplish both high film
strength and high processability. This concept of polymer design has been exported by licensing the PE production process and became a global standard for designing HDPE. Typically, we can see it as matt thin film in
supermarkets. It is a core concept for designing HDPE
even now and has been applied to other grades such as
pipe, bottle, and automobile fuel-tank grades.
The MgCl2-supported TiCl4 catalysts also innovated
the properties of LLDPE. Although LLDPE produced by
the TiCl3 catalysts had a considerably lower reputation
than LDPE, the MgCl2-supported TiCl4 catalysts converted the competitive situation between LLDPE and
LDPE completely. The innovatively improved LLDPE
by narrowing the composition distribution with the
MgCl2-supported TiCl4 catalysts was called the third
polyethylene and attracted much attention. Then, the
LLDPE market grew very rapidly by replacing such
materials as LDPE, paper, cloth, and glass. Furthermore,
the narrowed composition distribution enabled us to increase the comonomer content of LLDPE, leading to the
creation of new classes of PE called VLDPE and ULDPE
(having lower densities than LLDPE).
Figure 2. X-ray diffraction patterns of (A) MgCl2 and
(B) an MgCl2-supported TiCl4 catalyst.

pendently applied a patent about them on November 21


in the same year.8

PROGRESS IN PE PRODUCTION
Eventually, we succeeded to omit the de-ashing step
from the PE production process by developing MgCl2supported TiCl4 catalysts. It allowed us to simplify the
PE production plants and enlarge their scales, leading to
cutting the energy and production cost innovatively. We
have been licensing it worldwide since 1976 and replaced TiCl3 catalysts rapidly. MgCl2-supported TiCl4
catalysts not only enhanced the activity but also narrowed the molecular weight and composition distributions of PE. Significant improvement of the PE properties by narrowing them is easy to understand if you
imagine the recent improvement of the LLDPE properties by commercializing metallocene catalysts.9 The
MgCl2-supported TiCl4 catalysts were not single-site catalysts, but they allowed the active species to approach
the single-site nature. It enabled us to control PE structures precisely. Then, we designed a film-grade HDPE
consisting of a high-molecular-weight part having a high

PROGRESS IN PP PRODUCTION
The aforementioned MgCl2-supported TiCl4 catalyst
demonstrating extremely high activity in PE production
also was evaluated for PP production. In fact, the activity
was expectedly high even in propylene polymerization,
but we were disappointed at the very low stereoregularity
of the resulting PP. However, I noticed that it contained

Figure 3. Model for surface of an MgCl2-supported


TiCl4 catalyst.

HIGHLIGHT

Figure 4. Product design for an HDPE lm grade.

a considerable amount of high stereoregular PP (socalled iso-PP; insoluble in boiling heptane), and the
activity for producing the iso-PP part was 20 times as
high as that of the TiCl3 catalyst (as shown in Table 2).10
We expected it and tried various types of MgCl2supported TiCl4 catalysts for propylene polymerization. It resulted in similar results disappointing us with
the low stereoregularities, but we found that the stereoregularity changed by the kind of added compound
to destroy MgCl2 crystal. It might have shown that the
remaining compound on the MgCl2 surface acted as a
stereospecific improver, although we preferred that the
added compound had been displaced by the reaction
with TiCl4 to demonstrate the high activity in PE
production. Thus, we reached a new concept to introduce an organic compound called an electron donor
that could coordinate on the MgCl2 surface to improve
the stereospecificity and started to seek the effective
electron donors outside the MgCl2 crystal destroyers.
Here, we opened a new door that allowed us to get into
where an organic compound would control the stereoregularity of PP, whereas it had been done by the
inorganic crystal in the use of the TiCl3 catalyst. The
introduction of organic chemistry into the inorganic

world allowed us to design and control the active-site


structure by changing the organic compound and to
understand the drastic effects of MgCl2 that could be
considered as a huge ligand.
Eventually, we developed MgCl2-supported TiCl4
catalysts for PP production having higher stereospecificity than the TiCl3 catalysts, keeping 100 times higher
activity than those of the TiCl3 catalysts by introducing
an electron donor represented by ethyl benzoate (EB) as
shown in Table 3.11,12
The activity, called the rate of polymerization (Rp), is
given the product of the concentration of active sites
([C*]) and the chain-propagation rate (kp) at a given
monomer concentration ([M]), as in the following equation:
R pk p[C*][M]
Supporting TiCl4 on MgCl2 without EB increased both
[C*] and kp as shown in the middle column of Table 3.
The high specific surface area and TiCl4 located only on
the MgCl2 surface (as described above) could explain the
enormous enhancement of [C*]. The large enhancement
of kp was generally accepted as an electronic effect

Table 2. Propylene Polymerization Result with an MgCl2-Supported TiCl4 Catalyst System


Activity (g-PP/mmol-Ti h atm)
Catalyst System

Whole

Iso-PP

Ata-PP

I.I.(%)a

mm (%)b

MgCl2/TiCl4/Et3Al
TiCl3/Et3Al

968
23

328
17

640
6

33.9
75.9

89
91

a
b

Ratio of boiling heptane-insoluble part (iso-PP).


[mm] Measured with 13C NMR of iso-PP.

J. POLYM. SCI. PART A: POLYM. CHEM.: VOL. 42 (2004)


Table 3. Effects of MgCl2 and EB on Catalyst Performance

TiCl3-Et2AlCl
MgCl2/TiCl4-Et3Al
MgCl2/TiCl4/EB-Et3Al/EB

I.I. (%)

Specific
Activity

[C*] (mol %)

kp (L mol1 s1)

90
30
94

1
250
140

0.20.63
2060
2.8

2.5
240730
2700

brought about by MgCl2 as a kind of ligand effect. Doi et


al.13 proposed that electronic donation from MgCl2 to Ti,
where the electronegativity of Mg2 was smaller than
that of Ti3, brought about back-donation of d electrons
of Ti to the * orbital of propylene monomer, whereas
electrons of the monomer were donated to a vacant d
orbital in Ti, resulting in accretion of monomer insertion
into the growing polymer chain. The introduction of EB
considerably decreased [C*] as shown in the right-hand
column of Table 3 by deactivating selectively the active
sites producing ata-PP (aspecific sites). However, kp was
increased significantly by the addition of EB. It was
generally accepted that EB converted some of the aspecific sites to highly stereospecific sites, and kp at the
highly stereospecific sites was extremely higher than that
at the aspecific sites. We reported direct evidence of EB
transforming the aspecific sites into highly stereospecific
sites.14 We invested enormous effort to reveal the roles
and behavior of EB,1518 enabling us to discover more
effective electron donors (as described subsequently).
For example, Figure 5 demonstrates the relation of the
amount of EB and the activities. The addition of EB
decreased the activity for ata-PP and increased that for
iso-PP at an appropriate EB/Ti molar ratio, and it decreased even that for iso-PP at an excess addition of EB,
indicating the sensitive balance of the stereospecificity
improvement and the deactivation by EB. Besides, the
addition of EB increased the molecular weight of iso-PP,
suggesting the nature of the EB-participating highly stereospecific sites probably by the enhancement of kp.
A great deal of effort with electron donors represented
by EB established the platform of these PP production
technologies. The electron donors were classified into
two types, where one was an internal donor (ID) that was
supported on the MgCl2 surface with TiCl4 during catalyst preparation, and the other was an external donor
(ED) that was introduced with Et3Al at the start of
propylene polymerization. It was generally accepted that
ID was displaced from the catalyst surface by the reaction with Et3Al, and ED had a function of supplying
electron-donor molecules on the catalyst surface. By
finding such a combination, electron donors that had
been unable to be supported on MgCl2 during the catalyst
preparation because of its high reactivity with TiCl4 were

used for propylene polymerization. Through enormous


evaluation of electron donors, we eventually reached a
very effective combination of dialkyl phthalates and
alkoxysilanes as IDs and EDs, respectively.19 21 It was
confirmed2226 that a dialkyl phthalate as ID was displaced from the catalyst surface, and an alkoxysilane as
ED was fixed on the catalyst surface as a stereospecificity
improver instead of ID. The function of alkoxysilanes in
enhancing not only the stereospecificity but also the molecular weight of the resulting PP also was reported.27,28 Designing suitable structures of dialkyl phthalates and
alkoxysilanes gave us about 1000 times higher activity than
the TiCl3 catalysts and extremely high stereoregularity that
was more than 98% of I.I. Furthermore, the resulting PP did
not have any regio-irregularity except for its chain end. We
confirmed that regio-irregular insertions of the monomers
led to dormant sites that could be reactivated by chain
transfer by molecular hydrogen.29,30
It innovated the PP production process by dispensing
with the facilities and energy for removing the catalyst

Figure 5. Inuences of EB/Ti molar ratio in the


MgCl2-supported TiCl4 catalyst system on the yields of
overall polymer, iso-PP and ata-PP.

HIGHLIGHT

Figure 6. Simplication of industrial process for PP production.

residue and ata-PP as depicted in Figure 6. Nowadays, a


majority of industrial production of PP in the world is
carried out with this type of MgCl2-supported TiCl4 catalyst. Besides, they narrowed the molecular weight and composition distributions of PP as well as observed them in PE
production. It improved the qualities of random copolymers, creating heat-sealable film at low temperature, highperformance impact copolymer, and so forth.
Updating the catalyst preparation method also contributed significantly. Dissolving MgCl2 in a hydrocarbon completely for the reaction with TiCl4 enabled us to
control the particle size and morphology of the solid
catalyst precisely.31 Thus, the obtained catalyst possessed an excellent morphology with the aforementioned
high activity and high stereospecificity. The excellent
morphology allowed us to use the gas-phase process. The
gas-phase process not only cut the production costs down
but also contributed to the creation of the high-performance impact copolymer. To produce the impact copolymer, copolymerization of propylene and ethylene has to
be carried out after propylene homopolymerizarion to
blend PP and elastomer during copolymerization. The
gas-phase process could blend them uniformly because it
did not need any dispersion medium that would dissolve
the elastomer. The typical application of the high-performance impact copolymer is an automobile bumper that
used to be made of metal. Thus, the impact copolymers
have replaced metal and engineering plastics in such
applications as automobile and electric appliance parts.
We had collaborated with Montedison (now Basell) in
the development and licensing of MgCl2-supported TiCl4
catalysts for PP production for more than 20 years since
1975. As a result of our collaboration, more than a half of
the commercial PP plants in the world are our own or
licensing plants.

STATUS AND FUTURE DIRECTION


The stereoregularity of PP produced by the latest MgCl2supported TiCl4 catalyst reached 99.0% of [mmmm]
measured with 13C NMR. Figure 7 shows its stereoregularity distribution obtained by temperature-rising elution
fractionation (TREF) analysis as compared with that by
an MgCl2-supported TiCl4 catalyst having no electron
donors.32,33 In contrast with the latter that was a broad
and continuous distribution ranging from ata-PP to
highly isotactic PP, no polymer was eluted from the
former under 110 C, showing the absence of ata-PP.
Moreover, 35 wt % of the former was eluted over 130
C, whereas no polymer was eluted from the latter at that
region. Although 13C NMR analysis of this fraction was
carried out, [mmmm] of it was too high to determine the
value, namely, this fraction (35 wt % of the former) had
an almost perfect isotactic PP structure.

Figure 7. TREF proles of PPs prepared with MgCl2supported catalyst systems.

J. POLYM. SCI. PART A: POLYM. CHEM.: VOL. 42 (2004)

It showed both the strength and issue of the MgCl2supported TiCl4 catalyst. The strength is that the MgCl2supported TiCl4 catalyst is the only catalyst capable of
controlling stereoregularity of PP so precisely. However,
the issue is that it does not have a single-site nature. To
make a single-site nature while keeping its uniquely high
stereospecificity is one of the most important directions
for the future. Designing ED has brought about a narrow
molecular weight distribution (Mw/Mn) of 3.3.34
Another important direction for the future is to create
completely novel polymers such as hybrid polymers capable of compatibilizing immiscible polymers of crystal/
amorphous or polyolefin/polar polymer combinations.
Functionalized polyolefins are useful for synthesizing the
hybrid polymers with them as macromonomers, macroinitiators, or reactive polymers.35 MgCl2-supported TiCl4 catalysts can contribute to it as an example that they were able
to provide terminally hydroxylated iso-PP.36
We believe in a bright future for MgCl2-supported
TiCl4 catalysts as well as their brilliant progress.
The author thanks Shin-ichi Kojoh of Mitsui Chemicals
for his cooperation in preparing this review.

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