Process for the production of cycloolefin random copolymer

There is provided a process for the production of a cycloolefin copolymer which comprises copolymerizing an .alpha.-olefin having 2 or more carbon atoms and a specific cycloolefin in the presence of a specific metallocene type catalyst in a solvent mixture of a hydrocarbon solvent having a solubility parameter (value of .delta.) of 7.7 [(cal/cm.sup.3).sup.1/2 ] or more and a hydrocarbon solvent having a solubility parameter (value of .delta.) of 7.5 [(cal/cm.sup.3).sup.1/2 ] or less as a polymerization solvent. A cycloolefin copolymer having a high molecular weight can be produced in a high concentration by this process at a high yield.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a process for the production of a cycloolefin 
random copolymer. More specifically, it relates to a process for the 
production of a cycloolefin random copolymer, which permits the production 
of a cycloolefin-based random copolymer having a high molecular weight at 
a high yield. 
2. Prior Art 
A copolymer of ethylene and a specific bulky cycloolefin is a synthetic 
resin whose optical, mechanical and thermal properties are well balanced 
and used in the field of optical materials such as optical memory disks 
and optical fibers. It is already known that such a cycloolefin copolymer 
can be produced by copolymerizing ethylene and cycloolefin using a 
catalyst formed from (i) a transition metal compound, (ii) an organic 
aluminum oxy compound and/or a compound capable of forming an ionic 
complex when it reacts with a transition metal compound, and (iii) an 
organic aluminum compound as required. The copolymerization in such a 
catalytic system is usually carried out in a solvent having a high 
solubility parameter, such as toluene or benzene. However, when a 
cycloolefin copolymer having high heat resistance is to be synthesized in 
such a solvent, the proportion of the cycloolefin based on the total 
concentration of monomers in a polymerizer must be increased. Therefore, 
when .alpha.-olefin is ethylene, for example, it is impossible to raise 
the partial pressure of ethylene, thereby causing such problems as a 
reduction in polymerization speed, an incomplete reaction, and a large 
volume of cycloolefin to be recovered after polymerization. 
When a cycloolefin copolymer is to be synthesized in a solvent having a 
high solubility parameter in a high concentration, namely, 80 g/l or more, 
the viscosity of a polymerization system becomes high, thereby making it 
difficult to remove polymerization heat and maintain the uniform 
distribution of monomer components in the polymerization system, and 
lowering the transportability of a polymer solution. 
SUMMARY OF THE INVENTION 
It is therefore an object of the invention to provide a novel process for 
the production of a cycloolefin random copolymer 
It is another object of the present invention to provide a process for 
efficiently producing a cycloolefin random copolymer in a high 
concentration with a high polymerization rate. 
Further objects and advantages of the present invention will be apparent 
from the following description. 
According to the present invention, the above objects and advantages can be 
attained by a process for the production of a cycloolefin random copolymer 
which comprises copolymerizing (1) (i) an .alpha.-olefin having 2 or more 
carbon atoms and (ii) at least one cycloolefin selected from the group 
consisting of monomers represented by the following formula (I): 
##STR1## 
wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R.sup.1 to 
R.sup.18, R.sup.a and R.sup.b are independently selected from the group 
consisting of a hydrogen atom, halogen atom and hydrocarbon group, two out 
of R.sup.15 to R.sup.18 may jointly form a single hydrocarbon ring or 
multiple hydrocarbon rings including carbon atoms bonded thereto, and the 
single ring or multiple rings may have a double bond, and R.sup.15 and 
R.sup.16 or R.sup.17 and R.sup.18 may form an alkylidene group, and 
formula (II): 
##STR2## 
wherein p and q are each 0 or an integer of 1 or more, m and n are each 0, 
1 or 2, R.sup.1 to R.sup.19 are independently selected from the group 
consisting of a hydrogen atom, halogen atom, aliphatic hydrocarbon group, 
alicyclic hydrocarbon group, aromatic hydrocarbon group and alkoxy group, 
the carbon atom bonded to R.sup.9 and R.sup.10 and the carbon atom bonded 
to R.sup.13 or R.sup.11 may bonded together directly or through an 
alkylene group having 1 to 3 carbon atoms, and R.sup.15 and R.sup.12 or 
R.sup.15 and R.sup.19 may jointly form a monocyclic or polycyclic aromatic 
ring including carbon atoms bonded thereto when n=m=0, (2) in the presence 
of a catalyst formed from (i) a transition metal compound as a catalyst 
component (a) represented by the following formula (III): 
##STR3## 
wherein M.sup.1 is titanium, zirconium, hafnium, vanadium, niobium or 
tantalum, R.sup.1 and R.sup.2 are independently selected from the group 
consisting of a hydrogen atom, halogen atom, alkyl group having 1 to 10 
carbon atoms, alkoxy group having 1 to 10 carbon atoms, aryl group having 
6 to 10 carbon atoms, aryl oxy group having 6 to 10 carbon atoms, alkenyl 
group having 2 to 10 carbon atoms, aryl alkyl group having 7 to 40 carbon 
atoms, alkyl aryl group having 7 to 40 carbon atoms and aryl alkenyl group 
having 8 to 40 carbon atoms, R.sup.3 and R.sup.4 are independently a 
mononuclear or polynuclear hydrocarbon group having a cyclopentadienyl 
skeleton capable of forming a sandwich structure together with a central 
metal M.sup.1, and R.sup.5 is one of the following divalent groups: 
##STR4## 
in which R.sup.6, R.sup.7 and R.sup.8 are independently selected from the 
group consisting of a hydrogen atom, halogen atom, alkyl group having 1 to 
10 carbon atoms, fluoroalkyl group having 1 to 10 carbon atoms, fluoroaryl 
group having 6 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, 
alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 
carbon atoms, aryl alkyl group having 7 to 40 carbon atoms, alkyl aryl 
group having 7 to 40 carbon atoms and alkyl alkenyl group having 8 to 40 
carbon atoms, R.sup.6 and R.sup.7 or R.sup.6 and R.sup.8 may jointly form 
a ring including an atom bonded thereto, and M.sup.2 is silicon, germanium 
or tin, and (ii) at least one catalyst component (b) selected from the 
group consisting of organic aluminum oxy compounds and compounds capable 
of forming an ionic complex when they react with the above transition 
metal compound, (3) in a solvent mixture comprising (i) a hydrocarbon 
solvent having a solubility parameter (value of .delta.) of 7.7 
[(cal/cm.sup.3).sup.1/2 ] or more and (ii) a hydrocarbon solvent having a 
solubility parameter (value of .delta.) of 7.5 [(cal/cm.sup.3).sup.1/2 ] 
or less in a volume ratio [(i)/(ii)] of 99/1 to 50/50. 
The present invention is described in detail hereinunder. 
DETAILED DESCRIPTION OF THE INVENTION 
One of the monomers used in the process of the present invention is an 
.alpha.-olefin having 2 or more carbon atoms selected from .alpha.-olefins 
having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 
1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 
1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. These 
.alpha.-olefins may be used alone or in combination of two or more. Among 
these, ethylene is particularly preferred. 
The cycloolefin to be copolymerized with the above .alpha.-olefin is at 
least one compound represented by the above formula (I) or (II). 
In the formula (I), n is 0 or 1, m is 0 or a positive integer, and q is 0 
or 1. 
R.sup.1 to R.sup.18, R.sup.a and R.sup.b are independently selected from a 
hydrogen atom, halogen atom and hydrocarbon group. 
Illustrative examples of the halogen atom include fluorine, chlorine, 
bromine and iodine. Illustrative examples of the hydrocarbon group include 
alkyl group having 1 to 20 carbon atoms, halogenated alkyl group having 1 
to 20 carbon atoms, cycloalkyl group having 3 to 15 carbon atoms and 
aromatic hydrocarbon group having 6 to 20 carbon atoms. Specific examples 
of the alkyl group include methyl, ethyl, propyl, isopropyl, amyl, hexyl, 
octyl, decyl, dodecyl, octadecyl and the like. These alkyl groups may be 
substituted by a halogen atom. Specific examples of the cycloalkyl group 
include cyclohexyl group, and those of the aromatic hydrocarbon group 
include phenyl, naphthyl and the like. 
In the above formula (I), R.sup.15 and R.sup.16, R.sup.17 and R.sup.18, 
R.sup.15 and R.sup.17, R.sup.16 and R.sup.18, R.sup.15 and R.sup.18, or 
R.sup.16 and R.sup.17 may jointly form a monocyclic or polycyclic group 
including a carbon atom coupled thereto. The single ring or multiple rings 
thus formed may have a double bond. Specific examples of the single ring 
or multiple rings are as follows. 
##STR5## 
In the above examples, the carbon atoms numbered 1 and 2 are carbon atoms 
bonded to R.sup.15 (R.sup.16) or R.sup.17 (R.sup.18) in the formula (I), 
respectively. 
R.sup.15 and R.sup.16 or R.sup.17 and R.sup.18 may form an alkylidene 
group. The alkylidene group generally has 2 to 20 carbon atoms with 
examples thereof including ethylidene, propylidene and isopropylidene. 
In the above formula (II), p and q are each 0 or a positive integer, and m 
and n are each 0, 1 or 2. 
R.sup.1 to R.sup.19 are independently selected from the group consisting of 
a hydrogen atom, halogen atom, hydrocarbon group and alkoxy group. 
Examples of the halogen atom are the same as those of the halogen atom in 
the above formula (I). 
The hydrocarbon group is selected from alkyl group having 1 to 20 carbon 
atoms, cycloalkyl group having 3 to 15 carbon atoms and aromatic 
hydrocarbon group. Illustrative examples of the alkyl group include 
methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, 
octadecyl and the like. These alkyl groups may be substituted by a halogen 
atom. Examples of the cycloalkyl group include cyclohexyl. Examples of the 
aromatic hydrocarbon group include aryl group, aralkyl group and the like, 
more specifically, phenyl, tolyl, naphthyl, benzyl and phenylethyl. 
Illustrative examples of the alkoxy group include methoxy, ethoxy, propoxy 
and the like. 
In the formula (II), the carbon atom bonded to R.sup.9 and R.sup.10 and the 
carbon atom bonded to R.sup.13 or R.sup.11 may be bonded together directly 
or through an alkylene group having 1 to 3 carbon atoms. When the above 
two carbon atoms are bonded together through the alkylene group, the 
alkylene group is either one of methylene group (--CH.sub.2), ethylene 
group (--CH.sub.2 CH.sub.2 --) and trimethylene group (--CH.sub.2 CH.sub.2 
CH.sub.2 --). 
When n=m=0, R.sup.15 and R.sup.12 or R.sup.15 and R.sup.19 may jointly form 
a monocyclic or polycyclic aromatic ring including carbon atoms bonded 
thereto. Specifically, when n=m=0, the aromatic ring formed by R.sup.15 
and R.sup.12 is either one of the following rings (portions circled by 
broken lines). 
##STR6## 
In the above formulas, q is defined the same as in the formula (II). 
Illustrative examples of the cycloolefin represented by the above formula 
(I) or (II) are given below. 
Bicyclo[2.2.1]-2-heptene (commonly named norbornene) represented by the 
following formula: 
##STR7## 
wherein numerals 1 to 7 indicate position numbers of carbon atoms, and 
derivatives thereof in which the hydrogen atom of the compound is 
substituted by a hydrocaron group are first included in the examples. 
Illustrative examples of the hydrocarbon group include 5-methyl, 
5,6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 
5-phenyl, 5-methyl-5-phenyl, 5-benzyl, 5-tolyl, 5-(ethylphenyl), 
5-(isopropylphenyl), 5-(biphenyl), 5-(.beta.-naphthyl), 
5-(.alpha.-naphthyl), 5-(antracenyl), 5,6-diphenyl and the like. 
Illustrative examples of the derivatives include bicyclo[2.2.1]-2-heptene 
derivatives such as adduct of cyclopentadiene with acenaphthylene, 
1,4-methano-1,4,4a,9a-tetrahydrofluorene, 
1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene; tricyclo[4.3.0.1.sup.2,5 
]-3-decene derivatives such as tricyclo[4.3.0.1.sup.2,5 ]-3-decene, 
2-methyltricyclo[4.3.0.1.sup.2,5 ]-3-decene and 
5-methyltricyclo[4.3.0.1.sup.2,5 ]-3-decene; tricyclo[4.4.0.1.sup.2,5 
]-3-undecene derivatives such as tricyclo[4.4.0.1.sup.2,5 ]-3-undecene and 
10-methyltricyclo[4.4.0.1.sup.2,5 ]-3-undecene; and 
tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10 ]-3-dodecene represented by the 
following formula: 
##STR8## 
and derivatives thereof in which the hydrogen atom of the compound is 
substituted by a hydrocarbon group. 
Illustrative examples of the hydrocarbon group include 8-methyl, 8-ethyl, 
8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 
5,10-dimethyl, 2,10-dimethyl, 8,9-dimethyl, 8-ethyl-9-methyl, 
11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl-9-ethyl, 
9-isobutyl-2,7-dimethyl, 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 
9-isobutyl-11,12-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 
8-ethylidene-9-methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 
8-ethylidene-9-butyl, 8-n-propylidene, 8-n-propylidene-9-methyl, 
8-n-propylidene-9-ethyl, 8-n-propylidene-9-isopropyl, 
8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 
8-isopropylidene-9-ethyl, 8-isopropylidene-9-isopropyl, 
8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8,9-dichloro, 
8-phenyl, 8-methyl-8-phenyl, 8-benzyl, 8-tolyl, 8-(ethlphenyl), 
8-(isopropylphenyl), 8,9-diphenyl, 8-(biphenyl), 8-(.beta.-naphthyl), 
8-(.alpha.-naphthyl), 8-(anthracenyl)), 5,6-diphenyl and the like. 
Further examples of the derivatives include 
tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10 ]-3-dodecene derivatives such as 
adduct of (cyclopentadiene-acenaphthylene adduct) with cyclopentadiene, 
pentacyclo[6.5.1.1.sup.3,6.0.sup.2,7.0.sup.9,13 ]-4-pentadecene and 
derivatives thereof, pentacyclo[7.4.0.1.sup.2,5.1.sup.9,12.0.sup.8,13 
]-3-pentadecene and derivatives thereof, 
pentacyclo[8.4.0.1.sup.2,5.1.sup.9,12.0.sup.8,13 ]-3-hexadecene and 
derivatives thereof, pentacyclo[6.6.1.1.sup.3,6.0.sup.2,7.0.sup.9,14 
]-4-hexadecene and derivatives thereof, 
hexacyclo[6.6.1.1.sup.3,6.1.sup.10,13.0.sup.2,7.0.sup.9,14 ]-4-heptadecene 
and derivatives thereof, 
heptacyclo[8.7.0.1.sup.2,9.1.sup.4,7.1.sup.11,17.0.sup.3,8.0.sup.12,16 
]-5-eicosene and derivatives thereof, 
heptacyclo[8.7.0.1.sup.3,6.1.sup.10,17.1.sup.12,15.0.sup.2,7.0.sup.11,16 
]-4-eicosene and derivatives thereof, 
heptacyclo[8.8.0.1.sup.2,9.1.sup.4,7.1.sup.11,18.0.sup.3,8.0.sup.12,17 
]-5-heneicosene and derivatives thereof, 
octacyclo[8.8.0.1.sup.2,9.1.sup.4,7.1.sup.11,18.1.sup.13,16.0.sup.3,8.0.su 
p.12,17 ]-5-docosen and derivatives thereof, and 
nonacyclo[10.9.1.1.sup.4,7.1.sup.13,20.1.sup.15,18.0.sup.2,10.0.sup.3,8.0. 
sup.12,21.0.sup.14,19 ]-5-pentacosene and derivatives thereof. 
Illustrative examples of the cycloolefin represented by the general formula 
[I] or [II] have been given above, but the more concrete structures of 
these compounds are shown on pages 9 to 27 of European Patent Publication 
No. 0597119A1. These compounds can be used as a cycloolefin in the present 
invention. 
The cycloolefin represented by the above general formula (I) or (II) may be 
produced by subjecting an olefin having a structure corresponding to 
cyclopentadiene to a Diels-Alder reaction. 
Units derived from the cycloolefin represented by the above formula (I) or 
(II) and constituting a cycloolefin copolymer are considered to be 
represented by the following formula (I') or (II'). 
##STR9## 
wherein m, n, q, R.sup.1 to R.sup.16, R.sup.a and R.sup.b are defined the 
same as in the above formula (I). 
##STR10## 
wherein n, m, p, q and R.sup.1 to R.sup.19 are defined the same as in the 
above formula (II). 
The cycloolefins represented by the above formulas (I) and (II) may be used 
alone or in combination of two or more. 
Copolymerization of the above .alpha.-olefin and the cycloolefin in the 
process of the present invention is carried out in the presence of a 
specific catalyst formed from a transition metal compound as the 
afore-mentioned catalyst component (a), the catalyst component (b) and an 
organic aluminum compound as the catalyst component (c) as required. 
A detailed description is subsequently given of these catalyst components 
(a), (b) and (c). 
The transition metal compound as the catalyst component (a) is a compound 
represented by the above formula (III). In the formula (III), the 
transition metal M.sup.1 is titanium, zirconium, hafnium, vanadium, 
niobium or tantalum, of which zirconium and hafnium are preferred. 
In the formula (III) R.sup.1 and R.sup.2 are independently selected from 
the group consisting of a hydrogen atom, halogen atom, alkyl group having 
1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, aryl group 
having 6 to 10 carbon atoms, aryl oxy group having 6 to 10 carbon atoms, 
alkenyl group having 2 to 10 carbon atoms, aryl alkyl group having 7 to 40 
carbon atoms, alkyl aryl group having 7 to 40 carbon atoms, and aryl 
alkenyl group having 8 to 40 carbon atoms. 
Examples of the halogen atom include fluorine, chlorine, bromine and 
iodine. 
Examples of the alkyl group having 1 to 10 carbon atoms include methyl, 
ethyl, propyl, butyl, hexyl, octyl, decyl and the like. 
Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, 
ethoxy, propoxy, butoxy, hexoxy, octoxy, decyloxy and the like. 
Examples of the aryl group having 6 to 10 carbon atoms include phenyl, 
naphthyl and the like. 
Examples of the aryl oxy group having 6 to 10 carbon atoms include 
phenyloxy, naphthyloxy and the like. 
Examples of the alkenyl group having 2 to 10 carbon atoms include ethenyl, 
propenyl, 4-methyl-1-pentenyl, decenyl and the like. 
Examples of the alkyl aryl group having 7 to 40 carbon atoms include tolyl, 
ethylphenyl, propylphenyl, n-butylphenyl, t-butylphenyl and the like. 
Examples of the aryl alkyl group having 7 to 40 carbon atoms include 
benzyl, phenethyl, 1-phenylpropyl and the like. 
Examples of the aryl alkenyl group having 8 to 40 carbon atoms include 
phenylethylenyl and the like. 
In the above formula (III), R.sup.3 and R.sup.4 are each a mononuclear or 
polynuclear hydrocarbon group having a cyclopentadienyl skeleton capable 
of forming a sandwich structure with the central metal M.sup.1. 
Preferred examples of R.sup.3 and R.sup.4 include cyclopentadienyl group 
and substituents thereof, indenyl group and substituents thereof, and 
fluorenyl group and substituents thereof. Preferred combinations of 
R.sup.3 and R.sup.4 include a combination of cyclopentadienyl group or a 
substituent thereof and indenyl group or a substituent thereof, a 
combination of cyclopentadienyl group or a substituent thereof and 
fluorenyl group or a substituent thereof, and a combination of indenyl 
groups or substituents thereof. 
Further, in the above formula (III), R.sup.5 is a divalent group 
represented by the above formula. In the above formula, R.sup.6, R.sup.7 
and R.sup.8 can be each independently a group or atom as described above. 
A description is subsequently given of groups and atoms for R.sup.6, 
R.sup.7 and R.sup.8. 
Examples of the halogen atom include fluorine, chlorine, bromine and 
iodine. 
Preferred examples of the alkyl group having 1 to 10 carbon atoms include 
methyl, ethyl, propyl, butyl, hexyl, octyl, decyl and the like. 
Examples of the fluoroalkyl group having 1 to 10 carbon atoms include 
trifluoromethyl, pentafluoroethyl, octafluoropropyl and the like. 
Examples of the fluoroaryl group having 6 to 10 carbon atoms include 
pentafluorophenyl and the like. 
Examples of the aryl group having 6 to 10 carbon atoms include phenyl, 
naphthyl and the like. 
Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, 
ethoxy, propoxy, butoxy, hexoxy, octoxy, decyloxy and the like. 
Examples of the alkenyl group having 2 to 10 carbon atoms include ethenyl, 
propenyl, 4-methyl-1-pentenyl, decenyl and the like. 
Examples of the alkyl aryl group having 7 to 40 carbon atoms include tolyl, 
ethylphenyl, propylphenyl, n-butylphenyl, t-butylphenyl and the like. 
Examples of the aryl alkyl group having 7 to 40 carbon atoms include 
benzyl, phenethyl, 1-phenylpropyl and the like. 
Examples of the aryl alkenyl group having 8 to 40 carbon atoms include 
phenylethylenyl and the like. 
As described above; R.sup.6 and R.sup.7 or R.sup.6 and R.sup.8 may be 
bonded together to form a ring together with an atom bonded thereto. 
M.sup.2 is silicon, germanium or tin. 
Illustrative examples of the transition metal compound represented by the 
above formula (III) wherein the transition metal is zirconium are given 
below: 
isopropylidene(cyclopentadienyl-methylcyclopentadienyl)zirconium 
dichloride, 
isopropylidene(cyclopentadienyl-dimethylcyclopentadienyl)zirconium 
dichloride, 
isopropylidene(cyclopentadienyl-trimethylcyclopentadienyl)zirconium 
dichloride, 
isopropylidene(cyclopentadienyl-tetramethylcyclopentadienyl)zirconium 
dichloride, 
isopropylidene(cyclopentadienyl-ethylcyclopentadienyl)zirconium dichloride, 
isopropylidene(cyclopentadienyl-diethylcyclopentadienyl)zirconium 
dichloride, 
isopropylidene(cyclopentadienyl-triethylcyclopentadienyl)zirconium 
dichloride, 
isopropylidene(cyclopentadienyl-tetraethylcyclopentadienyl)zirconium 
dichloride, 
isopropylidene(cyclopentadienyl-fluorenyl)zirconium dichloride, 
isopropylidene(cyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
isopropylidene(cyclopentadienyl-octahydrofluorenyl)zirconium dichloride, 
isopropylidene(methylcyclopentadienyl-fluorenyl)zirconium dichloride, 
isopropylidene(dimethylcyclopentadienyl-fluorenyl)zirconium dichloride, 
isopropylidene(ethylcyclopentadienyl-fluorenyl)zirconium dichloride, 
isopropylidene(diethylcyclopentadienyl-fluorenyl)zirconium dichloride, 
isopropylidene(methylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
isopropylidene(dimethylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
isopropylidene(ethylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
isopropylidene(diethylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
isopropylidene(methylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
isopropylidene(dimethylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
isopropylidene(ethylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
isopropylidene(diethylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
cyclohexylidene(cyclopentadienyl-methylcyclopentadienyl)zirconium 
dichloride, 
cyclohexylidene(cyclopentadienyl-dimethylcyclopentadienyl)zirconium 
dichloride, 
cyclohexylidene(cyclopentadienyl-trimethylcyclopentadienyl)zirconium 
dichloride, 
cyclohexylidene(cyclopentadienyl-tetramethylcyclopentadienyl)zirconium 
dichloride, 
cyclohexylidene(cyclopentadienyl-ethylcyclopentadienyl)zirconium 
dichloride, 
cyclohexylidene(cyclopentadienyl-diethylcyclopentadienyl)zirconium 
dichloride, 
cyclohexylidene(cyclopentadienyl-triethylcyclopentadienyl)zirconium 
dichloride, 
cyclohexylidene(cyclopentadienyl-tetraethylcyclopentadienyl)zirconium 
dichloride, 
cyclohexylidene(cyclopentadienyl-fluorenyl)zirconium dichloride, 
cyclohexylidene(cyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
cyclohexylidene(cyclopentadienyl-octahydrofluorenyl)zirconium dichloride, 
cyclohexylidene(methylcyclopentadienyl-fluorenyl)zirconium dichloride, 
cyclohexylidene(dimethylcyclopentadienyl-fluorenyl)zirconium dichloride, 
cyclohexylidene(ethylcyclopentadienyl-fluorenyl)zirconium dichloride, 
cyclohexylidene(diethylcyclopentadienyl-fluorenyl)zirconium dichloride, 
cyclohexylidene(methylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
cyclohexylidene(dimethylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
cyclohexylidene(ethylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
cyclohexylidene(diethylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
cyclohexylidene(methylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
cyclohexylidene(dimethylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
cyclohexylidene(ethylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
cyclohexylidene(diethylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
diphenylmethylene(cyclopentadienyl-methylcyclopentadienyl)zirconium 
dichloride, 
diphenylmethylene(cyclopentadienyl-dimethylcyclopentadienyl)zirconium 
dichloride, 
diphenylmethylene(cyclopentadienyl-trimethylcyclopentadienyl)zirconium 
dichloride, 
diphenylmethylene(cyclopentadienyl-tetramethylcyclopentadienyl)zirconium 
dichloride, 
diphenylmethylene(cyclopentadienyl-ethylcyclopentadienyl)zirconium 
dichloride, 
diphenylmethylene(cyclopentadienyl-diethylcyclopentadienyl)zirconium 
dichloride, 
diphenylmethylene(cyclopentadienyl-triethylcyclopentadienyl)zirconium 
dichloride, 
diphenylmethylene(cyclopentadienyl-tetraethylcyclopentadienyl)zirconium 
dichloride, 
diphenylmethylene(cyclopentadienyl-fluorenyl)zirconium dichloride, 
diphenylmethylene(cyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
diphenylmethylene(cyclopentadienyl-octahydrofluorenyl)zirconium dichloride, 
diphenylmethylene(methylcyclopentadienyl-fluorenyl)zirconium dichloride, 
diphenylmethylene(dimethylcyclopentadienyl-fluorenyl)zirconium dichloride, 
diphenylmethylene(ethylcyclopentadienyl-fluorenyl)zirconium dichloride, 
diphenylmethylene(diethylcyclopentadienyl-fluorenyl)zirconium dichloride, 
diphenylmethylene(methylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
diphenylmethylene(dimethylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconiu 
m dichloride, 
diphenylmethylene(ethylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
diphenylmethylene(diethylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
diphenylmethylene(methylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
diphenylmethylene(dimethylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
diphenylmethylene(ethylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
diphenylmethylene(diethylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
dimethylsilylene(cyclopentadienyl-methylcyclopentadienyl)zirconium 
dichloride, 
dimethylsilylene(cyclopentadienyl-dimethylcyclopentadienyl)zirconium 
dichloride, 
dimethylsilylene(cyclopentadienyl-trimethylcyclopentadienyl)zirconium 
dichloride, 
dimethylsilylene(cyclopentadienyl-tetramethylcyclopentadienyl)zirconium 
dichloride, 
dimethylsilylene(cyclopentadienyl-ethylcyclopentadienyl)zirconium 
dichloride, 
dimethylsilylene(cyclopentadienyl-diethylcyclopentadienyl)zirconium 
dichloride, 
dimethylsilylene(cyclopentadienyl-triethylcyclopentadienyl)zirconium 
dichloride, 
dimethylsilylene(cyclopentadienyl-tetraethylcyclopentadienyl)zirconium 
dichloride, 
dimethylsilylene(cyclopentadienyl-fluorenyl)zirconium dichloride, 
dimethylsilylene(cyclopentadienyl-2,7-d-t-butylfluorenyl)zirconium 
dichloride, 
dimethylsilylene(cyclopentadienyl-octahydrofluorenyl)zirconium dichloride, 
dimethylsilylene(methylcyclopentadienyl-fluorenyl)zirconium dichloride, 
dimethylsilylene(dimethylcyclopentadienyl-fluorenyl)zirconium dichloride, 
dimethylsilylene(ethylcyclopentadienyl-fluorenyl)zirconium dichloride, 
dimethylsilylene(diethylcyclopentadienyl-fluorenyl)zirconium dichloride, 
dimethylsilylene(methylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
dimethylsilylene(dimethylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
dimethylsilylene(ethylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
dimethylsilylene(diethylcyclopentadienyl-2,7-di-t-butylfluorenyl)zirconium 
dichloride, 
dimethylsilylene(methylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
dimethylsilylene(dimethylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
dimethylsilylene(ethylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
dimethylsilylene(diethylcyclopentadienyl-octahydrofluorenyl)zirconium 
dichloride, 
isopropylidene(cyclopentadienyl-indenyl)zirconium dichloride, 
isopropylidene(methylcyclopentadienyl-indenyl)zirconium dichloride, 
isopropylidene(dimethylcyclopentadienyl-indenyl)zirconium dichloride, 
isopropylidene(ethylcyclopentadienyl-indenyl)zirconium dichloride, 
isopropylidene(diethylcyclopentadienyl-indenyl)zirconium dichloride, 
isopropylidene(cyclopentadienyl-benzoindenyl)zirconium dichloride, 
isopropylidene(cyclopentadienyl-tetrahydroindenyl)zirconium dichloride, 
isopropylidene(methylcyclopentadienyl-tetrahydroindenyl)zirconium 
dichloride, 
isopropylidene(dimethylcyclopentadienyl-tetrahydroindenyl)zirconium 
dichloride, 
isopropylidene(ethylcyclopentadienyl-tetrahydroindenyl)zirconium 
dichloride, 
isopropylidene(diethylcyclopentadienyl-tetrahydroindenyl)zirconium 
dichloride, 
dimethylsilylenebis(cyclopentadienyl)zirconium monohydride, 
dimethylsilylenebis(cyclopentadienyl)zirconium dichloride, 
dimethylsilylenebis(cyclopentadienyl)methylzirconium monochloride, 
dimethylsilylenebis(cyclopentadienyl)dimethylzirconium, 
dimethylsilylenebis(cyclopentadienyl)diphenylzirconium, 
silylenebis(cyclopentadienyl)zirconium dichloride, 
silylenebis(cyclopentadienyl)dimethylzirconium, 
diethylsilylenebis(cyclopentadienyl)zirconium dichloride, 
diethylsilylenebis(cyclopentadienyl)dimethyl zirconium, 
dimethylsilylenebis(methylcyclopentadienyl)zirconium dihydride, 
dimethylsilylenebis(indenyl)zirconium dichloride, 
dimethylsilylenebis(indenyl)zirconium monochloride monohydride, 
dimethylsilylenebis(indenyl)ethoxyzirconium chloride, 
dimethylsilylenebis(indenyl)dimethyl zirconium, 
dimethylsilylenebis(indenyl)diethyl zirconium, 
dimethylsilylenebis(indenyl)diphenyl zirconium, 
dimethylsilylenebis(indenyl)dibenzyl zirconium, 
dimethylsilylenebis(indenyl)methylzirconium monobromide, 
dimethylsilylenebis(indenyl)ethylzirconium monochloride, 
dimethylsilylenebis(indenyl)benzylzirconium monochloride, 
dimethylsilylenebis(indenyl)methylzirconium monochloride, 
dimethylsilylenebis(indenyl)zirconium dibromide, 
dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethyl zirconium, 
dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)ethyl zirconium ethoxide, 
dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, 
dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dibromide, 
dimethylsilylenebis(4-methyl-1-indenyl)zirconium dichloride, 
dimethylsilylenebis(5-methyl-1-indenyl)zirconium dichloride, 
dimethylsilylenebis(6-methyl-1-indenyl)zirconium dichloride, 
dimethylsilylenebis(7-methyl-1-indenyl)zirconium dichloride, 
dimethylsilylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, 
dimethylsilylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride, 
dimethylsilylenebis(4,7-dimethoxy-1-indenyl)zirconium dichloride, 
dimethylsilylenebis(indenyl)zirconium methoxide, 
dimethylsilylenebis(indenyl)zirconium diethoxide, 
dimethylsilylenebis(indenyl)methoxyzirconium chloride, 
dimethylsilylenebis(indenyl)ethoxyzirconium chloride, 
dimethylsilylenebis(indenyl)methylzirconium chloride, 
dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide, 
dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium ethoxide 
diethoxide, 
dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)methoxyzirconium chloride, 
dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, 
dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium ethoxide, 
dimethylsilylenebis(indenyl)zirconium dichloride, 
diethylsilylenebis(indenyl)dimethyl zirconium, 
dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, 
diethylsilylenebis(fluorenyl)zirconium dichloride, 
dimethylsilylenebis(fluorenyl)dimethyl zirconium, 
dimethylsilylenebis(fluorenyl)diphenyl zirconium, 
dimethylsilylenebis(fluorenyl)zirconium dichloride, 
dimethylsilylenebis(fluorenyl)diethyl zirconium, 
dimethylsilylenebis(fluorenyl)zirconium dichloride, 
ethylenebisindenylzirconium dichloride, 
ethylenebisindenylzirconium dibromide, 
ethylenebisindenyldimethylzirconium, 
ethylenebisindenyldiphenylzirconium, 
ethylenebisindenyldimethylzirconium monochloride, 
ethylenebisindenylzirconiumbis(methanesulfonate), 
ethylenebisindenylzirconiumbis(p-toluenesulfonate), 
ethylenebisindenylzirconiumbis(trifluoromethanesulfonate), 
and ethylenebistetrahydroindenylzirconium dichloride, 
Particularly preferred transition metal compounds are 
isopropylidene(cyclopentadienyl-fluorenyl)zirconium dichloride, 
isopropylidene(methylcyclopentadienyl-fluorenyl)zirconium dichloride, 
isopropylidene(isopropylcyclopentadienyl-fluorenyl)zirconium dichloride, 
isopropylidene(cyclopentadienyl-indenyl)zirconium dichloride, 
isopropylidene(cyclopentadienyl-benzoindenyl)zirconium dichloride, 
diphenylmethylene(cyclopentadienyl-indenyl)zirconium dichloride, and the 
like. 
Illustrative examples of the compound as the catalyst component (a) in 
which the transition metal is titanium, hafnium, vanadium, niobium or 
tantalum include compounds in which the central metals of the above 
zirconium compounds are substituted by these metals. 
These transition metal compounds may be carried on a carrier. 
The organic aluminum oxy compound used as the catalyst component (b) may be 
known aluminoxane or an organic aluminum oxy compound which is 
benzene-insoluble as described in U.S. Pat. No. 4,990,640. 
The known aluminoxane may be produced by the following processes, for 
example. 
(1) A process comprising adding an organic aluminum compound such as 
trialkyl aluminum to a hydrocarbon medium suspension of a compound 
containing absorbed water or a salt containing water of crystallization, 
such as magnesium chloride hydrate, copper sulfate hydrate, aluminum 
sulfate hydrate, nickel sulfate hydrate or cerium (III) chloride hydrate, 
and reacting these compounds; 
(2) a process comprising reacting an organic aluminum compound such as 
trialkyl aluminum directly with water or with ice or steam in a medium 
such as benzene, toluene, ethyl ether or tetrahydrofuran; and 
(2) a process comprising reacting an organic aluminum compound such as 
trialkyl aluminum with an organic tin oxide such as dimethyl tin oxide and 
dibutyl tin oxide in a medium such as decane, benzene or toluene. 
The aluminoxane may contain a slight amount of an organic metal component. 
After a solvent or an unreacted organic aluminum compound is removed from 
the above solution of aluminoxane by evaporation, the thus obtained 
aluminoxane may be redissolved in the solvent or suspended in a poor 
solvent of aluminoxane. 
Illustrative examples of the organic aluminum compound used in the 
preparation of aluminoxane include trialkyl aluminum such as trimethyl 
aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, 
tri-n-butyl aluminum, triisobutyl aluminum, tri-sec-butyl aluminum, 
tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl 
aluminum and tridecyl aluminum; tricycloalkyl aluminum such as 
tricyclohexyl aluminum and tricyclooctyl aluminum; dialkyl aluminum 
halides such as dimethyl aluminum chloride, diethyl aluminum chloride, 
diethyl aluminum bromide and diisobutyl aluminum chloride; dialkyl 
aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum 
hydride; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide 
and diethyl aluminum ethoxide; dialkyl aluminum aryloxides such as diethy 
aluminum phenoxide; and the like. 
Among these, trialkyl aluminum and tricycloalkyl aluminum are preferred, 
and trimethyl aluminum is particularly preferred. 
As the organic aluminum compound used in the preparation of aluminoxane, 
isoprenyl aluminum represented by the following general formula (IV) may 
also be used. 
EQU (i-C.sub.4 H.sub.3).sub.x Al.sub.y (C.sub.5 H.sub.10).sub.z(IV) 
wherein x, y and z are positive numbers which satisfy z.gtoreq.2x. 
The above organic aluminum compounds may be used alone or in combination of 
two or more. For instance, trimethyl aluminum and triisobutyl aluminum are 
used in combination. 
Illustrative examples of the solvent used in the preparation of aluminoxane 
include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and 
cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, 
decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons such 
as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; 
petroleum fractions such as gasoline, kerosene and gas oil; and halides of 
the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic 
hydrocarbons such as chlorides and bromides of these hydrocarbons. In 
addition, ethers such as ethyl ether and tetrahydrofuran may also be used. 
Among these, aromatic hydrocarbons and aliphatic hydrocarbons are 
particularly preferred. 
As the compound which can form an ionic complex when it reacts with a 
transition metal compound as the catalyst component (b), a compound 
comprising cations and anions formed by bonding a plurality of groups to 
an element, particularly a complex, may be preferably used. The compound 
comprising cations and anions formed by bonding a plurality of groups to 
an element may be preferably selected from compounds represented by the 
following formulas (V) and (VI): 
EQU ([L.sup.1 -R.sup.7 ].sup.k+).sub.p ([M.sup.3 Z.sup.1 Z.sup.2 . . . Z.sup.n 
].sup.(n-m)-).sub.q (V) 
EQU ([L.sup.2 ].sup.k+).sub.p ([M.sup.4 Z.sup.1 Z.sup.2 . . . Z.sup.n 
].sup.(n-m)-).sub.q (VI) 
wherein L.sup.1 is a Lewis base, M.sup.3 and M.sup.4 are each selected from 
groups VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA and VA of the periodic 
table, L.sup.2 is M.sup.5, R.sup.8 R.sup.9 M.sup.6, R.sup.10.sub.3 C or 
R.sup.11 M.sup.6, M.sup.5 and M.sup.6 are each selected from groups IIIB, 
IVB, VB, VIB, VIIB, VIII, IA, IB, IIA, IIB and VIIA of the periodic table, 
R.sup.8 and R.sup.9 are each selected from the group consisting of a 
cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group 
and fluorenyl group, R.sup.10 is selected from the group consisting of an 
alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon 
atoms, alkyl aryl group and aryl alkyl group, R.sup.11 is a large cyclic 
ligand such as tetraphenyl porphyrin and phthalocyanine, Z.sup.1 to 
Z.sup.n are each selected from the group consisting of a hydrogen atom, 
dialkyl amino group, alkoxy group having 1 to 20 carbon atoms, aryl oxy 
group having 6 to 20 carbon atoms, alkyl group having 1 to 20 carbon 
atoms, aryl group having 6 to 20 carbon atoms, alkyl aryl group, aryl 
alkyl group, halogen substituted hydrocarbon group having 1 to 20 carbon 
atoms, acyloxy group having 1 to 20 carbon atoms, organic metalloid group 
and halogen atom, two or more out of Z.sup.1 to Z.sup.n may be bonded 
together to form a ring, R.sup.7 is a hydrogen atom, alkyl group having 1 
to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkyl aryl 
group or aryl alkyl group, m is an integer of 1 to 7 representing a 
valence of M.sup.3 and M.sup.4, n is an integer of 2 to 8, k is an integer 
of 1 to 7 representing an ionic valency of [L.sup.1 -R.sup.7 ] and 
[L.sup.2 ], and p is an integer of 1 or more and satisfies 
q=(p.times.k)/(n-m). 
Illustrative examples of the Lewis base include amines such as ammonia, 
methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, 
diphenylamine, trimethylamine, triethylamine, tri-n-butylamine, 
N,N-dimethylaniline, methyldiphenylaniline, pyridine, 
p-bromo-N,N-dimethylaniline, p-nitro-N,N-dimethylaniline; phosphines such 
as triethylphosphine, triphenylphosphine and diphenylphosphine; ethers 
such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; 
thioethers such as diethyl thioether and tetrahydrothiophene; esters such 
as ethyl benzoate; and the like. 
Examples of M.sup.3 and M.sup.4 include B, Al, Si, P, As, Sb and the like, 
those of M.sup.5 include La, Na, Ag, Cu, Br, I, I.sup.3 and the like, and 
those of M.sup.6 include Mn, Fe, Co, Ni, Zn and the like. Examples of 
Z.sup.1 to Z.sup.n include dialkyl amino group such as dimethyl amino and 
diethyl amino; alkoxy group having 1 to 20 carbon atoms such as methoxy, 
ethoxy and n-butoxy; aryl oxy group having 6 to 20 carbon atoms such as 
phenoxy, 2,6-dimethyl phenoxy and naphthyloxy; alkyl group having 1 to 20 
carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, n-octyl 
and 2-ethylhexyl; aryl group having 6 to 20 carbon atoms, alkyl aryl group 
or aryl alkyl group such as phenyl, p-tolyl, benzyl, 4-t-butylphenyl, 
2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,4-dimethylphenyl and 
2,3-dimethylphenyl; halogen substituted hydrocarbon group having 1 to 20 
carbon atoms such as p-fluorophenyl, 3,5-difluorophenyl, 
pentachlorophenyl, 3,4,5-trifluorophenyl, pentafluorophenyl and 
3,5-di(trifluoromethyl)phenyl; halogen atom such as F, Cl Br and I; 
organic metalloid compounds such as pentamethyl antimony, trimethyl silyl, 
trimethylgermyl, diphenylarsine, dicyclohexylantimony and diphenyl boron; 
and the like. 
Examples of R.sup.7 and R.sup.10 are the same as those provided in the 
foregoing. As the substituted cyclopentadienyl group for R.sup.8 and 
R.sup.9, what is substituted by an alkyl group such as 
methylcyclopentadienyl, butylcyclopentadienyl or 
pentamethylcyclopentadienyl is used. The alkyl group has typically 1 to 6 
carbon atoms and the number of substituted alkyl groups is an integer of 1 
to 5. 
Among the compounds represented by the above formulas (V) and (VI), 
compounds in which M.sup.3 and M.sup.4 are boron are preferred. 
Among the compounds represented by the above formulas (V) and (VI), the 
following compounds may be particularly preferably used. 
Compounds of formula (V) 
triethylammonin tetraphenylborate, 
tri(n-butyl)ammonium tetraphenylborate, 
trimethylammonium tetraphenylborate, 
tetraethylammonium tetraphenylborate, 
methyltri(n-butyl)ammonium tetraphenylborate, 
benzyltri(n-butyl)ammonium tetraphenylborate, 
dimethyldiphenylammonium tetraphenylborate, 
methyltriphenylammonium tetraphenylborate, 
trimethylanilinium tetraphenylborate, 
methylpyridinium tetraphenylborate, 
benzylpyridinium tetraphenylborate, 
methyl(2-cyanopyridinium) tetraphenylborate, 
benzyldimethylsulfonium tetraphenylborate, 
trimethylsulfonium tetraphenylborate, 
triethylammonium tetra(pentafluorophenyl)borate, 
tri(n-butyl)ammonium tetra(pentafluorophenyl)borate, 
triphenylammonium tetra(pentafluorophenyl)borate, 
tetrabutylammonium tetra(pentafluorophenyl)borate, 
tetraethylammonium tetra(pentafluorophenyl)borate, 
methyltri(n-butyl)ammonium tetra(pentafluorophenyl)borate, 
benzyltri(n-butyl)ammonium tetra(pentafluorophenyl)borate, 
methyldiphenylammonium tetra(pentafluorophenyl)borate, 
methyltriphenylammonium tetra(pentafluorophenyl)borate, 
dimethyldiphenylammonium tetra(pentafluorophenyl)borate, 
anilinium tetra(pentafluorophenyl)borate, 
methylanilinium tetra(pentafluorophenyl)borate, 
dimethylanilinium tetra(pentafluorophenyl)borate, 
trimethylanilinium tetra(pentafluorophenyl)borate, 
dimethyl(m-nitroanilinium) tetra(pentafluorophenyl)borate, 
dimethyl(p-bromoanilinium) tetra(pentafluorophenyl)borate, 
pyridinium tetra(pentafluorophenyl)borate, 
(p-cyanopyridinium) tetra(pentafluorophenyl)borate, 
(N-methylpyridinium) tetra(pentafluorophenyl)borate, 
(N-benzylpyridinium) tetra(pentafluorophenyl)borate, 
(o-cyano-N-methylpyridinium) tetra(pentafluorophenyl)borate, 
(p-cyano-N-methylpyridinium) tetra(pentafluorophenyl)borate, 
(p-cyano-N-benzylpyridinium) tetra(pentafluorophenyl)borate, 
trimethylsulfonium tetra(pentafluorophenyl)borate, 
benzyldimethylsulfonium tetra(pentafluorophenyl)borate, 
tetraphenylsulfonium tetra(pentafluorophenyl)borate, 
dimethylanilinium tetra(3,5-ditrifluoromethylphenyl)borate, 
and triethylammonium hexafluoroarsenate. 
Compounds of formula (VII) 
ferrocenyl tetraphenylborate, 
silver tetraphenylborate, 
tritphenylcarmium tetraphenylborate, 
tetraphenylporphyrin manganese tetraphenylborate, 
ferrocenyl tetra(pentafluorophenyl)borate, 
1,1'-dimethylferrocenyl tetra(pentafluorophenyl)borate, 
decamethylferrocenyl tetra(pentafluorophenyl)borate, 
acetylferrocenyl tetra(pentafluorophenyl)borate, 
formylferrocenyl tetra(pentafluorophenyl)borate, 
cyanoferrocenyl tetra(pentafluorophenyl)borate, 
silver tetra(pentafluorophenyl)borate, 
triphenylcarbenium tetra(pentafluorophenyl)borate, 
lithium tetra(pentafluorophenyl)borate, 
sodium tetra(pentafluorophenyl)borate, 
tetraphenylporphyrin manganese 
tetra(pentafluorophenyl)borate, 
tetraphenylporphyrin (chloro) ferric 
tetra(pentafluorophenyl)borate, 
tetraphenylporphyrin zinc tetra(pentafluorophenyl)borate, 
silver tetrafluoroborate, 
silver tetrafluoroarsenate, and silver tetrafluoroantnonate. 
Compounds other than those of the formulas (V) and (VI) such as 
tri(pentafluorophenyl)boron, tri(3,5-di(trifluoromethyl)phenyl)boron, and 
triphenyl boron may also be used. 
The organic aluminum compound as the catalyst component (c) used as 
required in the present invention is an organic aluminum compound 
represented by the following general formula (VII): 
EQU R.sup.1.sub.n AlX.sub.3-n (VII) 
wherein R.sup.1 is a hydrocarbon group having 1 to 12 carbon atoms, X is a 
halogen atom or a hydrogen atom, and n is an integer of 1 to 3. 
In the above general formula (VII), R.sup.1 is a hydrocarbon group having 1 
to 12 carbon atoms, such as alkyl group, cycloalkyl group or aryl group. 
More specifically, it is selected from methyl, ethyl, n-propyl, isopropyl, 
isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl and 
the like. 
Specific examples of the organic aluminum compound include trialkyl 
aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl 
aluminum, triisobutyl aluminum, trioctyl aluminum and tri-2-ethylhexyl 
aluminum; alkenyl aluminum such as isoprenyl aluminum; dialkyl aluminum 
halides such as dimethyl aluminum chloride, diethyl aluminum chloride, 
diisopropyl aluminum chloride, diisobutyl aluminum chloride and dimethyl 
aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum 
sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum 
sesquichloride, butyl aluminum sesquichloride and ethyl aluminum 
sesquibromide; alkyl aluminum dihalides such as methyl aluminum 
dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and 
ethyl aluminum dibromide; alkyl aluminum hydrides such as diethyl aluminum 
hydride and diisobutyl aluminum hydride; and the like. 
As the organic aluminum compound, compounds represented by the following 
general formula (VIII) may also be used. 
EQU R.sup.1.sub.n AlY.sub.3-n (VIII) 
wherein n is 1 or 2, R.sup.1 is defined the same as in the above formula 
(VII), Y is a group represented by --OR.sup.2, --OSiR.sup.3.sub.3, 
--OAlR.sup.4.sub.2, --NR.sup.5.sub.2, --SiR.sup.6.sub.3 or 
--N(R.sup.7)AlR.sup.8.sub.2, R.sup.2, R.sup.3, R.sup.4 and R.sup.8 are 
each selected from the group consisting of a methyl group, ethyl group, 
isopropyl group, isobutyl group, cyclohexyl group and phenyl group, 
R.sup.5 is selected from the group consisting of a hydrogen atom, methyl 
group, ethyl group, isopropyl group, phenyl group and trimethyl silyl 
group, and R.sup.6 and R.sup.7 are each a methyl group or an ethyl group. 
Illustrative examples of the organic aluminum compound represented by the 
formula (VIII) include: 
(1) compounds represented by R.sup.1.sub.n Al(OR.sup.2).sub.3-n, such as 
dimethyl aluminum methoxide, diethyl aluminum ethoxide and diisobutyl 
aluminum methoxide; 
(2) compounds represented by R.sup.1.sub.n Al(OSiR.sup.3-3).sub.3-n, such 
as Et.sub.2 Al(OSiMe.sub.3), (iso-Bu).sub.2 Al(OSiMe.sub.3) and 
(iso-Bu).sub.2 Al(OSiEt.sub.3); 
(3) compounds represented by R.sup.1.sub.n Al(OAlR.sup.4.sub.2).sub.3-n, 
such as Et.sub.2 AlOAlEt.sub.2 and (iso-Bu).sub.2 AlOAl(iso-Bu).sub.2 ; 
(4) compounds represented by R.sup.1.sub.n Al(NR.sup.5.sub.2).sub.3-n, such 
as Me.sub.2 AlNEt.sub.2, Et.sub.2 AlNHMe, Me.sub.2 AlNEt, Et.sub.2 
AlN(SiMe.sub.3).sub.2 and (iso-Bu).sub.2 AlN(SiMe.sub.3).sub.2 ; 
(5) compounds represented by R.sup.1.sub.n Al(SiR.sup.6.sub.3).sub.3-n, 
such as (iso-Bu).sub.2 AlSiMe.sub.3 ; and 
(6) compounds represented by R.sup.1.sub.n 
Al(N(R.sup.7)AlR.sup.8.sub.2).sub.3-n, such as Et.sub.2 AlN(Me)AlEt.sub.2 
and (iso-Bu).sub.2 AlN(Et)Al(iso-Bu).sub.2. 
Among the organic aluminum compounds represented by the above general 
formulas (VII) and (VIII), the compounds represented by R.sup.1.sub.3 Al, 
R.sup.1.sub.n Al(OR.sup.2).sub.3-n and R.sup.1.sub.n 
Al(OAlR.sup.4.sub.2).sub.3-n are preferred, and compounds in which R.sup.1 
is an isoalkyl group and n is 2 are particularly preferred. 
As described above, the catalyst used in the process of the present 
invention contains a transition metal compound as the catalyst component 
(a), an organic aluminum oxy compound and/or a compound which is able to 
form an ionic complex when it reacts with a transition metal compound as 
the catalyst component (b), and an organic aluminum compound as the 
catalyst component (c) as required. The catalyst may contain other 
components useful for polymerization, in addition to these components. 
According to the process of the present invention, copolymerization between 
.alpha.-olefin and cycloolefin in the presence of the above catalyst is 
carried out in a mixture of hydrocarbon solvents having specific 
solubility parameters (value of .delta.). 
That is, according to the present invention, as the solvent used for 
copolymerization, a mixture of (i) a hydrocarbon solvent having a 
solubility parameter (value of .delta.) of 7.7 [(cal/cm.sup.3).sup.1/2 ] 
or more, preferably 7.7 to 8.7 [(cal/cm.sup.3).sup.1/2 ] and (ii) a 
hydrocarbon solvent having a solubility parameter (value of .delta.) of 
7.5 [(cal/cm.sup.3).sup.1/2 ] or less, preferably 7.4 
[(cal/cm.sup.3).sup.1/2 ] or less. 
Illustrative examples of the above solvent (i) having a solubility parmeter 
(value of .delta.) of 7.7 [(cal/cm.sup.3).sup.1/2 ] or more include the 
following compounds. 
______________________________________ 
solvent (i) value of .delta. 
______________________________________ 
toluene 8.9 
cyclopentane 8.7 
cyclohexane 8.2 
methylcyclohexane 
7.8 
______________________________________ 
Illustrative examples of the above solvent (ii) having a solubility 
parameter of 7.5 [(cal/cm.sup.3).sup.1/2 ] or less include the following 
compounds. 
______________________________________ 
solvent (ii) 
value of .delta. 
______________________________________ 
heptane 7.4 
n-hexane 
7.3 
n-pentane 
7.0 
n-butane 
6.8 
decane 6.6 
propane 6.4 
______________________________________ 
The above hydrocarbon solvents (i) and the above hydrocarbon solvents (ii) 
may be each used alone or in combination of two or more. 
The volume ratio [(i)/(ii)] of the hydrocarbon solvent (i) to the 
hydrocarbon solvent (ii) is 99/1 to 50/50, preferably 90/10 to 50/50, 
particularly preferably 85/15 to 60/40. 
Exemplary combinations of the hydrocarbon solvent (i) and the hydrocarbon 
solvent (ii) are as follows. 
cyclohexane/hexane 
cyclohexane/heptane 
cyclohexane/octane 
cyclohexane/decane 
methylcylohexane/hexane 
methylcylohexane/heptane 
methylcyclohexane/octane 
methylcyclohexane/decane 
According to the present invention, by carrying out copolymerization 
between .alpha.-olefin and cycloolefin in a mixture of the above 
hydrocarbon solvents (i) and (ii), the viscosity of a polymer solution can 
be reduced, polymerization heat can be easily removed, uniformity of 
monomer distribution in a polymerizer is improved and transportability of 
the polymer solution is enhanced. In addition, by using these specific 
hydrocarbon solvents, catalytic activity is not impaired and the degree of 
cycloolefin conversion is high. When a copolymer having the same molecular 
weight is to be produced by the process of the present invention, the 
copolymer can be produced in a higher concentration than the prior art. 
Further, when the copolymer is to be produced in a copolymer solution 
having the same concentration, a copolymer having a higher molecular 
weight can be produced than the prior art. Therefore, according to the 
present invention, a cycloolefin copolymer can be produced by a relatively 
simple means economically and at a high yield as a whole. 
To carry out the copolymerization of the present invention, the transition 
metal compound in the polymer solution is typically contained in an amount 
of 0.00005 to 1.0 mmol, preferably about 0.0001 to 0.3 mmol, based on 1 
liter of the polymer solution, and the organic aluminum oxy compound is 
used such that aluminum atoms in the organic aluminum oxy compound are 
typically contained in an amount of 1 to 10,000 mols, preferably 10 to 
5,000 mols, based on 1 mol of the transition metal atom contained in the 
transition metal compound, or the compound which can form an ionic complex 
when it reacts with a transition metal compound is used such that aluminum 
atoms are contained in an amount of 0.01 to 100 mols, preferably 0.5 to 5 
mols based on 1 mol of the transition metal atom. 
Polymerization temperature for carrying out the process of the present 
invention is typically -50.degree. to 230.degree. C., preferably 
-30.degree. to 200.degree. C., more preferably -20.degree. to 150.degree. 
C. Polymerization pressure is typically more than 0 to 100 kg/cm.sup.2 
.multidot.G, more preferably more than 0 to 50 kg/cm.sup.2 .multidot.G. A 
copolymerization reaction can be carried out in either one of batch, 
semi-continuous and continuous manners. Further, polymerization can be 
carried out in two or more steps which differ in reaction conditions. 
Reaction time (average residence time of a polymerization reaction mixture 
when copolymerization is carried out in a continuous manner), which 
differs according to types of monomers used, catalyst concentration and 
polymerization temperature, is typically 2 minutes to 5 hours, preferably 
5 minutes to 3 hours. 
According to the process for the production of a cycloolefin random 
copolymer of the present invention, use of a specific hydrocarbon solvent 
mixture described above as a copolymerization solvent suppresses an 
increase in the viscosity of the polymer solution, thereby making it easy 
to remove polymerization heat, maintain uniform distribution of monomer 
components in the system and transport the polymer solution. Since 
catalytic activity is not impaired by using this specific hydrocarbon 
solvent mixture, a cycloolefin copolymer can be produced at a high degree 
of cycloolefin conversion. As the result, a copolymer having a high 
molecular weight can be produced by a relatively simple means economically 
and at a high yield as a whole.

To further illustrate this invention, and not by way of limitation, the 
following examples are given. 
EXAMPLE 1 
preliminary activation of catalyst 
10.0 mg of isopropylidene (cyclopentadienyl-fluorenyl)zirconium dichloride 
was measured and mixed with a toluene solution of methylaluminoxane (to be 
abbreviated as MAO hereinafter) in a glass container fully substituted 
with nitrogen so that the final amount of aluminum atoms should be 9.25 
mmols (4.67 ml). The resulting solution was exposed to ultrasonic waves at 
23.degree. C. for 15 minutes and then diluted with 42.1 ml of toluene to 
prepare a catalyst solution. 
polymerization 
88.7 g of norbornene (to be abbreviated as NB hereinafter), 136.2 ml of 
toluene, 34.1 ml of n-hexane, and 0.3 ml of a toluene solution of 
triisobutyl aluminum (triisobutyl aluminum concentration: 1.0 mmol/ml) 
were added to a 1.5-liter autoclave which was dried under reduced pressure 
and substituted with nitrogen at normal temperature. Subsequently, the 
autoclave was pressurized to 4 kg/cm.sup.2 .multidot.G with ethylene under 
agitation and depressurized three times. The autoclave was then 
pressurized to 1.5 kg/cm.sup.2 .multidot.G with ethylene and temperature 
inside the autoclave was elevated to 70.degree. C. Thereafter, the 
autoclave was pressurized with ethylene to achieve an inner pressure of 6 
kg/cm.sup.2 .multidot.G. After 15 minutes of agitation, 3.03 ml of a 
toluene solution containing 
isopropylidene(cyclopentadienyl-fluorenyl)zirconium dichloride and MAO 
prepared in advance was added to the autoclave to start copolymerization 
between ethylene and NB. At this point, the addition was carried out in 
such a manner that the concentration of isopropylidene 
(cyclopentadienyl-fluorenyl)zirconium dichloride should be 0.005 mmol/ml 
and that of MAO 2.0 mmols/ml based on the polymer solution at the 
beginning of polymerization. Ethylene was supplied continuously during 
polymerization to maintain pressure inside the autoclave at 6 kg/cm.sup.2 
.multidot.G. After 60 minutes, a polymerization reaction was stopped by 
adding isopropyl alcohol. After depressurization, the polymer solution was 
taken out and contacted with an aqueous solution prepared by adding 5 ml 
of concentrated hydrochloric acid to 1 l of water in a ratio of 1:1 using 
a homomixer under agitation to shift the residual catalyst to a water 
phase. This contact solution mixture was left to stand and its water phase 
was separated and removed. Further, it was washed with distilled water two 
times to purify and separate a polymerization liquid phase. 
Thereafter, the purified and separated polymerization liquid phase was 
contacted with 3 volumes of acetone under strong agitation to deposit a 
copolymer. This solid (copolymer) was separated by filtration and washed 
completely with acetone. To extract unreacted TCD present in the polymer, 
the solid was injected into acetone in a solid/acetone ratio of 40 
g/liter. Thereafter, extraction was carried out at 60.degree. C. for 2 
hours. After the extraction, the solid was separated by filtration and 
dried at 130.degree. C. at 350 mmHg for 12 hours under nitrogen air 
stream. 
The yield of an ethylene/NB copolymer thus obtained was 55.5 g, its 
intrinsic viscosity [.eta.] measured in a decaline solvent at 135.degree. 
C. was 1.3 dl/g, its glass transition temperature Tg was 110.degree. C., 
its NB content was 47.4 mol %, and its catalyst activity was 37,000 g/mmol 
Zr. Results obtained are shown in Table 1. 
EXAMPLE 2 
Copolymerization was carried out in the same manner as in Example 1 except 
that ethylene was supplied in such a manner that pressure inside the 
autoclave at the time of copolymerization was maintained at 10 kg/cm.sup.2 
.multidot.G. Results obtained are shown in Table 1. 
EXAMPLE 3 
Copolymerization was carried out in the same manner as in Example 1 except 
that a mixture of cyclohexane and n-hexane (volume ratio of 80/20) was 
used as a polymerization solvent. Results obtained are shown in Table 1. 
EXAMPLE 4 
Copolymerization was carried out in the same manner as in Example 1 except 
that a mixture of cyclohexane and n-hexane (volume ratio of 70/30) was 
used as a polymerization solvent. Results obtained are shown in Table 1. 
COMATIVE EXAMPLE 1 
Copolymerization was carried out in the same manner as in Example 1 except 
that toluene was used alone as a polymerization solvent. Results obtained 
are shown in Table 1. Compared with the case where a solvent mixture was 
used (Example 1), the intrinsic viscosity [.eta.] and molecular weight of 
the copolymer were small and Tg of the copolymer was low. 
COMATIVE EXAMPLE 2 
Copolymerization was carried out in the same manner as in Example 1 except 
that n-hexane was used alone as a polymerization solvent. Results obtained 
are shown in Table 1. A copolymer became insoluble during polymerization 
and the polymer solution was whitened. Compared with the case where a 
solvent mixture was used (Example 1), the catalyst activity of the 
copolymer was low and its yield was small. 
TABLE 1 
__________________________________________________________________________ 
ethylene 
solvent value of .delta. 
ratio 
type of 
pressure 
Zr 
(i)/(ii) (i)/(ii) 
(i)/(ii) 
cycloolefin (g) 
(kg/cm.sup.2 G) 
(mM/L) 
__________________________________________________________________________ 
Example 1 
toluene/n-hexane 
8.9/7.3 
80/20 
NB 88.7 
6 0.005 
Example 2 
toluene/n-hexane 
8.9/7.3 
80/20 
NB 88.7 
10 0.005 
Example 3 
cyclohexane/n-hexane 
8.2/7.3 
80/20 
NB 88.7 
6 0.005 
Example 4 
cyclohexane/n-hexane 
8.2/7.3 
70/30 
NB 88.7 
6 0.005 
Comparative 
toluene 8.9 100/0 
NB 88.7 
6 0.005 
Example 1 
Comparative 
n-hexane 7.3 0/100 
NB 88.7 
6 0.005 
Example 2 
__________________________________________________________________________ 
content of 
MAO TIBA yield 
activity 
Tg [.eta.] 
cycloolefin 
(mM/L) 
(mM/L) 
(g) 
(g/mMZr) 
(.degree.C.) 
(dl/g) 
(mol %) 
__________________________________________________________________________ 
Example 1 
2.0 4.0 55.5 
37,000 110 
1.31 47.4 
Example 2 
2.0 4.0 72.0 
48,000 93 
1.33 38.5 
Example 3 
2.0 4.0 57.0 
38,000 128 
1.41 46.9 
Example 4 
2.0 4.0 58.5 
39,000 131 
1.35 47.3 
Comparative 
2.0 4.0 52.5 
35,000 95 
1.29 38.4 
Example 1 
Comparative 
2.0 4.0 27.0 
18,000 145 
1.37 49.7 
Example 2 
__________________________________________________________________________