Catalyst component for polymerization of alpha-olefins and process for producing alpha-olefin polymers using the same

A catalyst component for the polymerization of alpha-olefins, represented by the following formula [I]: ##STR1## wherein R.sup.1 -R.sup.3 =H, a halogen, a C.sub.1-10 hydrocarbon radical, a Si-containing C.sub.1-18 hydrocarbon radical, or a halogen-containing C.sub.1-10, hydrocarbon radical (provided that R.sup.1 and R.sup.2 cannot be hydrogen at the same time); n=2 to 7; Q=a C.sub.1-20 hydrocarbon radical, a silylene or oligosilylene group having or not having a C.sub.1-20 hydrocarbon radical, a germylene group having or not having a C.sub.1-20 hydrocarbon radical; X and Y=H, a halogen, a C.sub.1-20 hydrocarbon radical, or an O- or N-containing C.sub.1-20 hydrocarbon radical; and M=a transition metal selected from the groups IVB-VIB; a catalyst for the polymerization of alpha-olefins, comprising the catalyst component; and a process for producing alpha-olefin polymers, where use is made of the catalyst. Use of the catalyst will produce alpha-olefin polymers having a high melting point and a high molecular weight in a high yield.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a catalyst component for use in the 
polymerization of alpha-olefins. More specifically, the present invention 
relates to a catalyst component for the polymerization of alpha-olefins 
and a catalyst for the same comprising the catalyst component, which make 
it possible to produce alpha-olefin polymers having a high melting point, 
and to a process for producing alpha-olefin polymers using the catalyst. 
2. Related Art 
The so-called Kaminsky catalysts (metallocene catalysts) are well known as 
homogeneous catalysts for the polymerization of olefins. These catalysts 
are characterized in that they have extremely high polymerization activity 
and that they are useful for the production of polymers having a narrow 
molecular-weight distribution. 
Ethylenebis(indenyl)zirconium dichloride and 
ethylenebis-(4,5,6,7-tetrahydroindenyl)zirconium dichloride have been 
known as transition-metal compounds which are used when isotactic 
polyolefins are produced by the use of the Kaminsky catalysts (Japanese 
Laid-Open Patent Publication No. 130314/1986). However, these compounds 
appear to have shortcomings in that the polyolefins obtained have a low 
molecular weight and that when the polymerization is carried out at low 
temperatures, high-molecular-weight polyolefins can be obtained, but the 
compounds cannot show high polymerization activity. Further, it has also 
been known that polyolefins having a high molecular weight can be obtained 
when those compounds which are prepared by replacing the zirconium in the 
above transition-metal compounds with hafnium are used (Journal of 
Molecular Catalysis, 56 (1989), pp. 237-247). However, this method seems 
to he disadvantageous in that high polymerization activity would not be 
expected. 
Furthermore, dimethylsilylenebis-substituted cyclopenta-dienylzirconium 
dichloride and the like were proposed in Japanese Laid-Open Patent 
Publication No. 301704/1989, Polymer Preprints, Japan, Vol. 39, No. 6, pp. 
1614-1616 (1990) and Japanese Laid-Open Patent Publication No. 12406/1991, 
and dimethylsilylenebis(indenyl)zirconium dichloride and the like were 
proposed in Japanese Laid-Open Patent Publications Nos. 295007/1988 and 
275609/1989. By these catalysts, it was made possible to obtain 
highly-stereoregular polymers having a high melting point if the 
polymerization is carried out at relatively low temperatures. However, 
when polymerization is carried out under the condition of higher 
temperatures, which is economically advantageous, the polymers obtained 
would have a stereoregularity, a melting point and a molecular weight 
significantly lowered. For this reason, it is demanded to improve the 
catalysts. 
Japanese Laid-Open Patent Publications Nos. 268307/1992 and 268308/1992 
suggest that the stereoregularity and molecular weight of polymers can be 
improved to some extent when use is made as a catalyst of a compound 
having a substituent attached at a site next to the site of the 
crosslinking group (the 2-position) in the above-described 
cyclopentadienyl compound. Further, Japanese Laid-Open Patent Publications 
Nos. 300887/1992, 306304/1993, 100579/1994, 184179/1994 and 157661/1994 
suggest that polymers having improved properties can be obtained when use 
is made as a catalyst of a metallocene compound having a substituent 
attached to the indenyl group. However, the properties of those polymers 
which are produced by the use of these substituted compounds under the 
polymerization condition of elevated temperatures, which condition is 
economically advantageous, are seemed to be still insufficient. 
An object of the present invention is to provide a catalyst component for 
the polymerization of alpha-olefins and a catalyst for the same, which 
make it possible to produce, in high yield, high-molecular-weight olefin 
polymers capable of being extrusion- or injection-molded, having a high 
melting point, and a process for producing alpha-olefin polymers. 
SUMMARY OF THE INVENTION 
The present invention has been accomplished as a result of the studies 
which were made in order to solve the aforementioned problems in the prior 
art. 
The present invention provides a catalyst component for use in the 
polymerization of alpha-olefins which comprises a compound represented by 
the following general formula [I]: 
##STR2## 
wherein R.sup.1, R.sup.2 and R.sup.3 each independently represent 
hydrogen, a halogen, a hydrocarbon radical having 1 to 10 carbon atoms, a 
silicon-containing hydrocarbon radical having 1 to 18 carbon atoms, or a 
halogen-containing hydrocarbon radical having 1 to 10 carbon atoms, 
provided that at least one of R.sup.1 and R.sup.2 is the radical other 
than hydrogen; n is an integer of 2 to 7; Q is a divalent group which 
combines the two 5-membered rings, and represents a hydrocarbon radical 
having 1 to 20 carbon atoms, a silylene or oligosilylene group, a silylene 
or oligosilylene group containing a hydrocarbon radical having 1 to 20 
carbon atoms, a germylene group, or a germylene group containing a 
hydrocarbon radical having 1 to 20 carbon atoms; X and Y each 
independently represent hydrogen, a halogen, a hydrocarbon radical having 
1 to 20 carbon atoms, or an oxygen- or nitrogen-containing hydrocarbon 
radical having 1 to 20 carbon atoms; and M represents a transition metal 
selected from the groups IVB to VIB in the Periodic Table. 
Further, the present invention relates to a catalyst for the polymerization 
of alpha-olefins, comprising the above-defined catalytic component. 
Namely, the catalyst for the polymerization of alpha-olefins according to 
the present invention comprises the following components (A) and (B) in 
combination: 
Component (A) which is the above-defined catalyst component for the 
polymerization of alpha-olefins; and 
Component (B) which is (a) an aluminum oxy compound, (b) a Lewis acid, or 
(c) an ionic compound which can react with the Component (A) to convert 
the Component (A) into a cation. 
Furthermore, the present invention relates to a process for producing 
alpha-olefin polymers, where use is made of the above-defined catalyst. 
Namely, the process for producing alpha-olefin polymers according to the 
present invention comprises the step of contacting an alpha-olefin into 
contact with a catalyst comprising the following Components (A) and (B) in 
combination, thereby polymerizing the alpha-olefin: 
Component (A) which is the above-defined catalyst component for the 
polymerization of alpha-olefins; and 
Component (B) which is (a) an aluminum oxy compound, (b) a Lewis acid, or 
(c) an ionic compound which can react with the Component (A) to convert 
the Component (A) into a cation. 
By the use of the catalyst of the present invention, alpha-olefin polymers 
having a high melting point and a high molecular weight can be produced in 
high yield. 
Although it is not clear why such advantages inherent in the present 
invention are attained, the following may be considered as the reason for 
it (however, the present invention is not restricted by the following 
theory). Namely, in contrast to a conventional metallocene compound having 
such a ligand as an indenyl group that has a ring formed with conjugate 
double bonds contiguous to and fused with a 5-membered ring, the compound 
having the formula [I] of the present invention is such that the 
substituents on the ring contiguous to and fused with a 5-membered ring, 
namely, R.sup.1 and R.sup.2, at the 4-position, namely, the position at 
which R.sup.1 and R.sup.2 are bonded, project upward and downward at right 
angles or a proper angle to the plane on which the condensing ring lies. 
It is therefore presumed that since these substituents act as steric 
hindrance groups which regulate the direction of polymer chains to grow 
and that of the coordination of monomers, the polymer obtained is to have 
improved stereoregularity, and, as a result, to have a higher melting 
point. 
Further, when the conventional metallocene compound has a ligand whose 
5-membered cyclic compound moiety is 4,5,6,7-tetra-hydroindenyl group, 
which corresponds to the compound represented by the formula [I] in which 
both R.sup.1 and R.sup.2 are hydrogen and n is 3, and when such a compound 
is used as a catalyst component in polymerization which is carried out at 
a higher temperature, a polymer having a drastically-lowered melting point 
tends to be obtained. In contrast, in the case of the compound [I] of the 
present invention, a change in the stereostructure of the compound would 
be prevented due to the existence of the substituents at the 4-position. 
Therefore, a polymer having a melting point which is not lowered can be 
obtained even when the compound is used in polymerization which is carried 
out at a higher temperature. 
We believe that the above-described effects of the present invention would 
be unexpected from the prior art. 
DESCRIPTION OF THE PREFERRED EMBODIMENT OF THE INVENTION 
The present invention relates to a catalyst component for polymerization, 
comprising a compound represented by the formula [I] which will be 
described later in detail. Further, the present invention relates to a 
catalyst for the polymerization of alpha-olefins, which comprises a 
catalyst component for polymerization comprising in combination Component 
(A), which is a compound represented by the formula [I], and Component (B) 
which will be described later in detail; and to a process for producing 
alpha-olefin polymers, comprising the step of contacting an alpha-olefin 
with this catalyst, thereby polymerizing the alpha-olefin. The terms 
"comprising" and "comprising in combination" used herein mean that 
compounds or components which are not mentioned herein can also be used in 
combination with those which are mentioned as long as they do not impair 
the advantages inherent in the present invention. 
&lt;Component (A)&gt; 
The catalyst component (A) of the present invention is a transition-metal 
compound represented by the following formula [I]: 
##STR3## 
wherein R.sup.1, R.sup.2 and R.sup.3 each independently represent 
hydrogen, a halogen, a hydrocarbon radical having 1 to 10 carbon atoms, a 
silicon-containing hydrocarbon radical having 1 to 18 carbon atoms, or a 
halogen-containing hydrocarbon radical having 1 to 10 carbon atoms, 
provided that at least one of R.sup.1 and R.sup.2 is the radical other 
than hydrogen; n is an integer of 2 to 7; Q is a divalent group which 
combines the two 5-membered rings, and represents a hydrocarbon radical 
having 1 to 20 carbon atoms, a silylene or oligosilylene group, a silylene 
or oligosilylene group containing a hydrocarbon radical having 1 to 20 
carbon atoms, a germylene group, or a germylene group containing a 
hydrocarbon radical having 1 to 20 carbon atoms; X and Y each 
independently represent hydrogen, a halogen, a hydrocarbon radical having 
1 to 20 carbon atoms, or an oxygen- or nitrogen-containing hydrocarbon 
radical having 1 to 20 carbon atoms; and M represents a transition metal 
selected from the groups IVB to VIB in the Periodic Table. 
The metallocene compound having the formula [I] for use in the present 
invention is characterized in that the two 5-membered cyclic ligands 
having the substituents R.sup.1, R.sup.2 and R.sup.3 are, as the formula 
[I] shows, asymmetric with respect to a plane on which M, X and Y lie in 
view of the relative position through the group Q, in other words, the two 
5-membered cyclic ligands facing each other with a plane on which M, X and 
Y lie therebetween are not in the relationship between an object and its 
mirror image with respect to the plane. 
R.sup.1, R.sup.2 and R.sup.3 are as mentioned above. More specifically, 
R.sup.1, R.sup.2 and R.sup.3 each independently represent (a) hydrogen, 
(b) a halogen, specifically chlorine, bromine, fluorine or the like, (c) a 
hydrocarbon radical having 1 to 10 carbon atoms, for example, (i) a 
saturated hydrocarbon radical, specifically, alkyl, cycloalkyl or the 
like, more specifically, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, 
n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, 
cyclohexyl, cyclooctyl or the like, or (ii) an unsaturated hydrocarbon 
radical, specifically, alkenyl, aryl or the like, more specifically, 
vinyl, allyl, phenyl, tolyl, naphthyl or the like, (d) a 
silicon-containing hydrocarbon radical having 1 to 18 carbon atoms, for 
example, an alkylsilyl, arylsilyl, alkylsilylalkyl or arylsilylalkyl 
group, specifically, dimethylsilyl, trimethylsilyl, triethylsilyl, 
triphenylsilyl, dimethylsilylmethyl, bis(trimethylsilyl)methyl or the 
like, or (e) a halogen-containing hydrocarbon radical, for example, a 
haloalkyl or haloaryl group, specifically, chloromethyl, trichloromethyl, 
trifluoromethyl, p-fluorophenyl, pentafluorophenyl or the like. 
Of these groups enumerated as R.sup.1, R.sup.2 and R.sup.3, an alkyl group 
having 1 to 4 carbon atoms (for example, methyl, ethyl, n-propyl, 
i-propyl, cyclopropyl, n-butyl, i-butyl, t-butyl, etc.), an aryl group 
(for example, phenyl, tolyl, naphthyl, etc.), a silyl group (for example, 
trimethylsilyl, triphenylsilyl, etc.), and a fluorinated hydrocarbon 
radical (for example, trifluoromethyl, pentafluorophenyl, etc.) are 
preferred. An alkyl group having 1 to 4 carbon atoms, and an aryl group 
having 6 to 10 carbon atoms are more preferred. 
As mentioned previously, it is an essential condition that at least either 
one of R.sup.1 and R.sup.2 be the radical other than hydrogen, that is, 
R.sup.1 and R.sup.2 are not hydrogen at the same time. 
n is an integer of 2 to 7, preferably 3 to 7, more preferably 4 to 7. 
Therefore, the condensing ring formed by (CH.sub.2).sub.n with two vicinal 
carbon atoms contained in the 5-membered ring is a 5- to 10-membered ring, 
preferably a 6- to 10-membered ring. More preferably, n is an integer of 4 
to 7, and the condensing ring is a 7-membered ring or larger. 
Q is a divalent group which combines the two conjugated 5-membered rings, 
and represents, for example, (a) a divalent hydrocarbon radical having 1 
to 20, preferably 1 to 6 carbon atoms, more specifically, a saturated or 
unsaturated hydrocarbon radical such as an alkylene, cycloalkylene or 
arylene group, (b) a silylene or oligosilylene group, (c) a silylene or 
oligosilylene group containing a hydrocarbon radical having 1 to 20, 
preferably 1 to 12 carbon atoms, (d) a germylene group, or (e) a germylene 
group containing a hydrocarbon radical having 1 to 20, preferably 1 to 12 
carbon atoms. Of these, alkylene, cycloalkylene, arylene and alkylsilylene 
groups are preferred. It is preferable that the length of the group Q, 
namely the distance between the sites of Q, at which the two 5-membered 
rings are combined, irrespective of the number of carbon atoms contained 
in Q, be, when Q is linear, equal to the size of approximately 4 atoms or 
less, in particular, 2 atoms or less, and when Q has a cyclic group, equal 
to the size of the cyclic group plus approximately 2 atoms or less, in 
particular, the size of the cyclic group only. Therefore, in the case 
where Q is an alkylene group, ethylene and isopropylidene where the length 
of Q is equal to the size of 2 atoms and that of 1 atom, respectively, are 
preferred; in the case where Q is a cycloalkylene group, cyclohexylene 
where the length is equal to the size of the cyclohexylene group only is 
preferred; in the case where Q is an alkylsilylene group, dimethysilylene 
where the length is equal to the size of 1 atom is preferred; and in the 
case where Q is an arylsilylene group, diphenylsilylene where the length 
is again 1 atom is preferred. 
X and Y each independently (that is, X and Y may be the same or different) 
represent (a) hydrogen, (b) a halogen (specifically, fluorine, chlorine, 
bromine or iodine, preferably chlorine), (c) a hydrocarbon radical having 
1 to 20, preferably 1 to 10 carbon atoms, or (d) an oxygen- or 
nitrogen-containing hydrocarbon radical having 1 to 20, preferably 1 to 10 
carbon atoms. Of these, hydrogen, chlorine, methyl, isobutyl, phenyl, 
benzyl, dimethylamino, diethylamino are preferred. 
M is a transition metal selected from the groups IVB to VIB in the Periodic 
Table, preferably titanium, zirconium or hafnium which is a transition 
metal selected from the group IVB, more preferably zirconium. 
The compound [I] of the present invention can be synthesized by any process 
as long as it is suitable for introducing the desired substituents or for 
forming the desired bonding. A typical route for the synthesis of the 
compound is as follows. It is noted that HRa shown in the synthesis route 
represents a compound having the following formula: 
##STR4## 
HR.sup.a +n-C.sub.4 H.sub.9 Li.fwdarw.R.sup.a Li+n-C.sub.4 H.sub.10 
2R.sup.a Li+QCl.sub.2 .fwdarw.Q(R.sup.a).sub.2 +2LiCl 
Q(R.sup.a).sub.2 +2.cndot.n-C.sub.4 H.sub.9 Li.fwdarw.Q (R.sup.b Li).sub.2 
+2.cndot.n-C.sub.4 H.sub.10 
(wherein HR.sup.b R.sup.a) 
Q(R.sup.b Li).sub.2 +ZrCl.sub.4 .fwdarw.Q(R.sup.b).sub.2 ZrCl.sub.2 +2LiCl 
Non-limitative examples of the above transition-metal compound are as 
follows. Although the following compounds are simply described by their 
chemical names, it is a matter of course that they are of the asymmetric 
structure as herein defined in this Specification. 
(1) Ethylenebis(4-methyl-4,5,6,7-tetrahydroindenyl)-zirconium dichloride, 
(2) Ethylenebis(4,4-dimethyl-4,5,6,7-tetrahydroindenyl)-zirconium 
dichloride, 
(3) Ethylenebis(2,4-dimethyl-4,5,6,7-tetrahydroindenyl)-zirconium 
dichloride, 
(4) Ethylenebis(2,4,4-trimethyl-4,5,6,7-tetrahydro-indenyl)zirconium 
dichloride, 
(5) Ethylenebis(4-methylhexahydroazulenyl)zirconium dichloride, 
(6) Ethylenebis(4,4-dimethylhexahydroazulenyl)zirconium dichloride, 
(7) Ethylenebis(2,4-dimethylhexahydroazulenyl)zirconium dichloride, 
(8) Ethylenebis(2,4,4-trimethylhexahydroazulenyl)-zirconium dichloride, 
(9) Ethylenebis(2-methyl-4-phenylhexahydroazulenyl)-zirconium dichloride, 
(10) Ethylenebis(2-methyl-4-isopropylhexahydroazulenyl)-zirconium 
dichloride, 
(11) 
Ethylenebis(9-bicyclo[6.3.0]undeca-2-methyl-2,3,4,5,6,7-hexahydropentaenyl 
)zirconium dichloride, 
(12) 
Ethylenebis(9-bicyclo[6.3.0]2,10-dimethylundeca-2,3,4,5,6,7-hexahydropenta 
enyl)zirconium dichloride, 
(13) 
Ethylenebis(9-bicyclo[6.3.0]2,2,10-trimethyl-undeca-2,3,4,5,6,7-hexahydrop 
entaenyl)zirconium dichloride, 
(14) 
Ethylenebis(11-bicyclo[8.3.0]2,12-dimethyltrideca-2,3,4,5,6,7,8,9-octahydr 
ohexaenyl)zirconium dichloride, 
(15) 
Ethylenebis(11-bicyclo[8.3.0]2,2,12-trimethyl-trideca-2,3,4,5,6,7,8,9-octa 
hydrohexaenyl)zirconium dichloride, 
(16) Methylenebis(2,4-dimethyl-4,5,6,7-tetrahydro-indenyl)zirconium 
dichloride, 
(17) Methylenebis(2,4,4-trimethyl-4,5,6,7-tetrahydro-indenyl)zirconium 
dichloride, 
(18) Methylenebis(2,4,4-trimethyl-hexahydroazulenyl)-zirconium dichloride, 
(19) Isopropylidenebis(2,4-dimethyl-4,5,6,7-tetrahydro-indenyl)zirconium 
dichloride, 
(20) Isopropylidenebis(2,4,4-trimethyl-4,5,6,7-tetra-hydroindenyl)zirconium 
dichloride, 
(21) Isopropylidenebis(2,4,4-trimethyl-hexahydro-azulenyl)zirconium 
dichloride, 
(22) Cyclohexylidenebis(2,4-dimethyl-4,5,6,7-tetrahydro-indenyl)zirconium 
dichloride, 
(23) 
Cyclohexylidenebis(2,4,4-trimethyl-4,5,6,7-tetra-hydroindenyl)zirconium di 
chloride, 
(24) Cyclohexylidenebis(2,4,4-trimethyl-hexahydro-azulenyl)zirconium 
dichloride, 
(25) 
1,2-Diphenylethylenebis(2,4-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium 
dichloride, 
(26) 
1,2-Diphenylethylenebis(2,4,4-trimethyl-4,5,6,7-tetrahydroindenyl)zirconiu 
m dichloride, 
(27) 1,2-Diphenylethylenebis(2,4,4-trimethyl-hexa-hydroazulenyl)zirconium 
dichloride, 
(28) Dimethylsilylenebis(4-methyl-4,5,6,7-tetrahydro-indenyl)zirconium 
dichloride, 
(29) Dimethylsilylenebis(4-phenyl-4,5,6,7-tetrahydro-indenyl)zirconium 
dichloride, 
(30) Dimethylsilylenebis(4,4-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium 
dichloride, 
(31) Dimethylsilylenebis(2,4-dimethyl-4,5,6,7-tetrahydro-indenyl)zirconium 
dichloride, 
(32) 
Dimethylsilylenebis(2,4,4-trimethyl-4,5,6,7-tetra-hydroindenyl)zirconium 
dichloride, 
(33) Dimethylsilylenebis(4-methylhexahydroazulenyl)-zirconium dichloride, 
(34) Dimethylsilylenebis(4,4-dimethylhexahydroazulenyl)-zirconium 
dichloride, 
(35) Dimethylsilylenebis(4,4-diphenylhexahydroazulenyl)-zirconium 
dichloride, 
(36) Dimethylsilylenebis(2,4-dimethylhexahydroazulenyl)-zirconium 
dichloride, 
(37) Dimethylsilylenebis(2,4,4-trimethylhexahydro-azulenyl)zirconium 
dichloride, 
(38) Dimethylsilylenebis(2-methyl-4-phenyl-hexahydro-azulenyl)zirconium 
dichloride, 
(39) Dimethylsilylenebis(2-methyl-4-isopropylhexahydro-azulenyl)zirconium 
dichloride, 
(40) Dimethylsilylenebis(2-methyl-4,4-diphenylhexahydro-azulenyl)zirconium 
dichloride, 
(41) 
Dimethylsilylenebis(9-bicyclo[6.3.0]undeca-2-methyl-2,3,4,5,6,7-hexahydrop 
entaenyl)zirconium dichloride, 
(42) 
Dimethylsilylenebis(9-bicyclo[6.3.0]2,10-dimethyl-undeca-2,3,4,5,6,7-hexah 
ydropentaenyl)zirconium dichloride, 
(43) 
Dimethylsilylenebis(9-bicyclo[6.3.0]2,2,10-trimethylundeca-2,3,4,5,6,7-hex 
ahydropentaenyl)zirconium dichloride, 
(44) 
Dimethylsilylenebis(11-bicyclo[8.3.0]2,12-dimethyl-trideca-2,3,4,5,6,7,8,9 
-octahydrohexaenyl)zirconium dichloride, 
(45) 
Dimethylsilylenebis(11-bicyclo[8.3.0]2,2,12-trimethyltrideca-2,3,4,5,6,7,8 
,9-octahydrohexaenyl)zircon ium dichloride, 
(46) 
Phenylmethylsilylenebis(2,4-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium 
dichloride, 
(47) 
Phenylmethylsilylenebis(2,4,4-trimethyl-4,5,6,7-tetrahydroindenyl)zirconiu 
m dichloride, 
(48) Phenylmethylsilylenebis(2,4,4-trimethylhexahydro-azulenyl)zirconium 
dichloride, 
(49) Diphenylsilylenebis(2,4-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium 
dichloride, 
(50) 
Diphenylsilylenebis(2,4,4-trimethyl-4,5,6,7-tetrahydroindenyl)zirconium di 
chloride, 
(51) Diphenylsilylenebis(2,4,4-trimethylhexahydro-azulenyl)zirconium 
dichloride, 
(52) Dimethylgermylenebis(2,4-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium 
dichloride, 
(53) 
Dimethylgermylenebis(2,4,4-trimethyl-4,5,6,7-tetrahydroindenyl)zirconium 
dichloride, and 
(54) Dimethylgermylenebis(2,4,4-trimethylhexahydro-azulenyl)zirconium 
dichloride. 
It is noted that the nomenclature was based on "Nomenclature in Organic 
Chemistry and Life Chemistry (Book One)" edited by Kenzo Hirayama and 
Kazuo Hirayama, published by Nankodo, Japan. 
Further, those compounds which are obtainable by replacing one of or both 
of the chlorides in the above-enumerated compounds with bromine, iodine, 
hydrogen, methyl, phenyl, benzyl, alkoxy, dimethylamide, diethylamide or 
the like can also be mentioned. 
Furthermore, those compounds which are obtainable by replacing the 
zirconium in the above-enumerated compounds with titanium, hafnium, 
tantalum, niobium, vanadium, tungsten, molybdenum or the like can also be 
mentioned. Of these compounds, preferable ones are those in which M is 
titanium, zirconium or hafnium, which is a transition metal selected from 
the group IVB, and more preferable ones are those in which M is zirconium. 
Of these compounds, those in which one phenyl radical is attached to the 
4-position or those in which two hydrocarbon radicals are attached to the 
4-position are preferred. Further, tetrahydroindenyl group (n=3), 
hexahydroazulenyl group (n=4), and octahydro[6.3.0]undeca-pentaenyl group 
(n=8) are more preferred, hexahydroazulenyl being most preferred. 
&lt;Component (B)&gt; 
The Component (B) is (a) an aluminumoxy compound, (b) a Lewis acid or (c) 
an ionic compound which can react wiith the Component (A) to convert the 
Component (A) into a cation. 
Some of the Lewis acids can also be regarded as "an ionic compound which 
can react with the Component (A) to convert the Component (A) into a 
cation." Thus, a compound belonging to both of "a Lewis acid" and "an 
ionic compound which can react with the Component (A) to convert the 
Component (A) into a cation" should be considered to belong to one of the 
two. 
The aluminumoxy compounds (a) specifically include those represented by the 
formulae [II], [III] or [IV]. 
##STR5## 
wherein p denotes a numeral of 0-40, preferably 2-30, R.sup.1 s represent 
hydrogen or a hydrocarbon group having preferably 1-10 carbon atoms, more 
preferably 1-6 carbon atoms. 
The compounds [II] and [III] are also called alumoxanes, which are obtained 
by the reaction of a trialkylaluminum or two or more types of a 
trialkylaluminum with water. Specific examples include (i) products 
obtained from a trialkylaluminum and water such as methylalumoxane, 
ethylalumoxane, propylalumoxane, butylalumoxane and isobutylalumoxane, and 
(ii) products obtained from two types of a trialkylaluminum and water such 
as methylethylalumoxane, methylbutylalumoxane and methylisobutylalumoxane. 
Among those, the particularly preferred are methylalumoxane and 
methylisobutylalumoxane. 
These alumoxanes can be used in combination thereof within the group (II) 
or (III) and/or between the groups of (II) and (III). It is also possible 
to use these alumoxanes in combination with another alkylaluminum compound 
such as trimethylaluminum, triethylaluminum, triisobutylaluminum or 
dimethylaluminum chloride. 
These alumoxanes can be prepared under a variety of well-known conditions. 
Specifically, there can be mentioned the following methods: 
(i) a method wherein trialkylaluminum is directly reacted with water in the 
presence of an appropriate organic solvent such as toluene, benzene or 
ether; 
(ii) a method wherein a trialkylaluminum is reacted with a salt hydrate 
containing water of crystallization such as a hydrate of copper sulfate or 
aluminum sulfate; 
(iii) a method wherein a trialkylaluminum is reacted with moisture 
supported on silica gel or the like which has been impregnated with water; 
(iv) a method wherein trimethylaluminum and another alkylaluminum e.g. 
triisobutylaluminum in admixture are directly reacted with water in the 
presence of an appropriate organic solvent such as toluene, benzene or 
ether; 
(v) a method wherein trimethylaluminum and triisobutylaluminum in admixture 
are reacted under heating with a salt hydrate containing water of 
crystallization such as a hydrate of copper sulfate or aluminum sulfate; 
(vi) a method wherein silica gel is impregnated with water, treated with 
triisobutylaluminum, followed by additional treatment with 
trimethylaluminum; 
(vii) a method wherein methylalumoxane and isobutylalumoxane are 
synthesized by known method, these alkylalumoxanes are admixed in a 
certain amount and then subjected to reaction under heating; and 
(viii) a method wherein a salt having water of crystallization such as 
copper sulfate pentahydrate to an aromatic hydrocarbon solvent such as 
benzene or toluene and the salt is then reacted with trimethylaluminum at 
a temperature of about -40 to 40.degree. C. In this case, the amount of 
water used is in a molar ratio of 0.5-1.5 to trimethylaluminum. 
Methylalumoxane thus obtained is a linear or cyclic organoaluminum polymer 
of formula [II] or [III]. 
The compound [IV] can be obtained by reacting a trialkylaluminum or two or 
more trialkylaluminums with a alkylboronic acid represented by the formula 
EQU R.sup.5 B--(OH).sub.2 
wherein R.sup.5 represents a hydrocarbon group having 1-10 carbon atoms, 
preferably 1-6 carbon atoms, in a molar ratio of 10:1-1:1. Specific 
examples of the compound of the formula [IV] include (i) a reaction 
product of trimethylaluminum and methylboronic acid in a ratio of 2:1, 
(ii) a reaction product of triisobutylaluminum and methylboronic acid in a 
ratio of 2:1, (iii) a reaction product of trimethylaluminum, 
triisobutylaluminum and methylboronic acid in a ratio of 1:1:1, (iv) a 
reaction product of trimethylaluminum and ethylboronic acid in a ratio of 
2:1, and (v) a reaction product of triethylaluminum and butylboronic acid 
in a ratio of 2:1. The compound [IV] can be used as a mixture thereof, and 
it can also be used in combination with the another alkylaluminum compound 
such as trimethylaluminum, triethylaluminum, triisobutylaluminum or 
dimethylaluminum chloride. 
The ionic compound (c) which can react with the Component (A) convert the 
latter into a cation includes a compound represented by the formula: 
EQU [K].sup.e+ [Z].sup.e- [V] 
wherein K represents a cationic component having an ionic charge and 
includes for example a carbonium cation, a tropylium cation, an ammonium 
cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and 
the like. There are also mentioned a cation of a metal which tends to be 
reduced itself or a cation of an organometal. These cations specifically 
include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, 
indenium, triethylammonium, tripropylammonium, tributylammonium, 
N,N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, 
triphenylphosphonium, trimethylphosphonium, tri(dimethylphenyl) 
phosphonium, tri(methylphenyl)phosphonium, triphenylsulfonium, 
triphenyloxonium, triethyloxonium, pyrilium, a silver ion, a gold ion, a 
platinum ion, a copper ion, a palladium ion, a mercury ion, a ferrocenium 
ion, and the like. 
Z in the formula [V] represents an anionic component having an ionic 
charge, which will be a counter anion (generally non-coordinated) against 
a cationic species derived from the Component (A), and includes for 
example an organoboron compound anion, an organoaluminum compound anion, 
an organogallium compound anion, an organophosphorus compound anion, an 
organoarsenic compound anion, an organoantimony compound anion, and the 
like. The anionic components specifically include 
(i) tetraphenylboron, tetrakis(3,4,5-trifluorophenyl )boron, 
tetrakis(3,5-di(trifluoromethyl)phenyl)boron, 
tetrakis(3,5-di(tert-butyl)phenyl)boron, tetrakis(pentafluorophenyl)boron, 
(ii) tetraphenylaluminum, tetrakis(3,4,5-trifluorophenyl)aluminum, 
tetrakis(3,5-di(trifluoromethyl)phenyl)aluminum, tetrakis 
(3,5-di(tert-butyl)phenyl)aluminum, tetrakis(pentafluorophenyl)aluminum, 
(iii) tetraphenylgallium, tetrakis(3,4,5-trifluorophenyl)gallium, 
tetrakis(3,5-di(trifluoromethyl)phenyl)gallium, 
tetrakis(3,5-di(tert-butyl)phenyl)gallium, 
tetrakis(pentafluorophenyl)gallium, (iv) tetraphenylphosphorus, 
tetrakis(pentafluorophenyl)phosphorus, (v) tetraphenylarsenic, 
tetrakis(pentafluorophenyl)-arsenic, 
(vi) tetraphenylantimony, tetrakis(pentafluorophenyl)antimony, (vii) a 
decaborate, an undecaborate, a carbadodecaborate, a decachlorodecaborate, 
and the like. 
As a Lewis acid (b), particularly the one which can convert the Component 
(A) into a cation, there are illustrated a variety of organoboron 
compounds, metal halide compounds, and solid acids. Specifically, there 
can be mentioned (i) an organoboron compound such as triphenylboron, 
tris(3,5-difluorophenyl)boron and tris(pentafluorophenyl)boron; (ii) a 
metal halide compound such as aluminum chloride, aluminum bromide, 
aluminum iodide, magnesium chloride, magnesium bromide, magnesium iodide, 
magnesium chlorobromide, magnesium chloroiodide, magnesium bromoiodide, 
magenesium chloride hydride, magnesium chloride hydroxide, magnesium 
bromide hydroxide, magnesium chloride alkoxides and magnesium bromide 
alkoxides, (iii) a solid acid such as silica-alumina and alumina. 
These ionic compounds and the Lewis acids can be used solely or in 
combination with the aluminumoxy compounds represented by the formula 
[II], [III] or [IV]. These compounds can also be used in combination with 
an organoaluminum compound such as a tri-lower alkylaluminum, a di-lower 
alkylaluminum monohalide, a mono-lower alkylaluminum dihalide and a lower 
alkylaluminum sesquihalide as well as a derivative thereof in which a part 
of these lower alkyl groups has been replaced by a phenoxy group, examples 
of which include trimethylaluminum, triethylaluminum, triisobutylaluminum, 
diethylaluminum phenoxide and dimethylaluminum chloride. 
&lt;Making up Catalysts&gt; 
The catalyst of the present invention can be prepared by bringing the above 
described Components (A) and (B) into contact in the presence or absence 
of a monomer to be polymerized in or outside a polymerization vessel. 
The Components (A) and (B) may be used in any suitable amounts in the 
present invention. For instance, in the case of solvent polymerization, 
the Component (A) is preferably used in an amount of 10.sup.-7 -10.sup.2 
mmole/liter, more preferably 10.sup.-4 -1 mmole/liter based on the 
transition metal atom. In the case where the Component (B) is the 
aluminumoxy compound, the molar ratio of Al/transition metal is preferably 
in the range from 10 or more to 100,000 or less, more preferably from 100 
or more to 20,000 or less, particularly from 100 or more to 10,000 or 
less. On the other hand, when the ionic compound or the Lewis acid is used 
as the Component (B), the ratio of the Component (B)/the Component (A) on 
the basis of the transition metal is in the range of 0.1-1,000, preferably 
0.5-100, more preferably 1-50. 
The catalyst of the present invention can, as described above, contain 
other components or ingredients in addition to the Components (A) and (B). 
The third component as an optional ingredient which can be incorporated in 
addition to the Components (A) and (B) include for example an active 
hydrogen-containing compound such as H.sub.2 O , methanol, ethanol and 
butanol, an electron-donating compound such as an ether, an ester or an 
amine, and an alkoxy containing compound such as phenyl borate, 
dimethylmethoxy-aluminum, phenyl phosphite, tetraethoxysilane and 
diphenyldimethoxysilane. 
When these catalysts are used in the polymerization of an olefin, the 
Components (A) and (B) may be separately introduced into a reaction 
vessel, or the Components (A) and (B) which have been previously brought 
into contact with each other may be introduced into a reaction vessel. 
When the Components (A) and (B) are previously brought into contact with 
each other, it is also possible to carry out the contact in the presence 
of a monomer to be polymerized in order to partially polymerize the 
monomer, that is to subject the catalyst to preliminary polymerization. 
It is also possible to bring the Components (A) and (B) and a porous 
carrier, for example an inorganic porous carrier such as silica, alumina 
or magnesium chloride, or an organic porous carrier such as polypropylene, 
polystyrene or polydivinylbenzene into contact in a desired sequence and 
to use the mixture as a supported catalyst. 
&lt;Use of Catalyst/Polymerization of Olefins&gt; 
The catalyst according to the present invention can be applied not only to 
the solvent polymerization with a solvent, but also to the liquid phase 
solvent-free polymerization, the vapor phase polymerization or the molten 
polymerization wherein no solvent is substantially used. In addition, it 
is applied to the continuous polymerization or the batch-wise 
polymerization. As the solvent in the solvent polymerization, saturated 
aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, 
cyclohexane, benzene or toluene are used alone or as a mixture thereof. 
Polymerization temperature is in the range of from -78 to ca. 200.degree. 
C., preferably from -20 to 100.degree. C. The pressure of the olefin in 
the reaction system is not specifically limited, but it is preferably in 
the range of atmospheric pressure to 50 kg/cm.sup.2. G. 
During polymerization, it is possible to control the molecular weight by 
the well-known means such as the selection of temperature or pressure, or 
the introduction of hydrogen. 
.alpha.-Olefins to be polymerized with the catalyst of the present 
invention, that is to say, the .alpha.-olefins including ethylene used for 
the polymerization reaction in the process of the present invention are 
.alpha.-olefins having 2-20 carbon atoms, preferably 2-10 carbon atoms. 
The .alpha.-olefins include specifically propylene, 1-butene, 
4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 
1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and the like. The 
catalyst of the present invention is preferably used for the 
polymerization of an .alpha.-olefin having 3-10 carbon atoms for the 
purpose of the stereospecific polymerization, particularly for the 
polymerization of propylene. These .alpha.-olefins can be subjected to 
polymerization as a mixture thereof. 
Furthermore, the catalyst of the present invention can be used for 
polymerizing the above described higher .alpha.-olefin with ethylene, and 
it can be effectively used also for the copolymerization of the other 
monomers copolymerizable with the above described .alpha.-olefins 
including conjugated and non-conjugated dienes such as butadiene, 
1,4-hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene and 1,9-decadiene, 
and cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, 
norbornene and dicyclopentadiene.

The present invention is illustrated further specifically with reference to 
the following non-limitative examples. 
EXAMPLE 1 
&lt;Synthesis of 
Dimethylsilylenebis(2,4-dimethyl-hexahydro-azulenyl)-zirconium dichloride&gt; 
2-Methylazulene was synthesized in accordance with the method described in 
Japanese Laid-Open Patent Publication No. 207232/1987. Thus, 19.5 g (0.16 
mol) of tropolone and 40 g (0.21 mol) of p-toluenesulfonic acid chloride 
were reacted with each other in pyridine to obtain 37.1 g of tosylated 
tropolone. This compound was then reacted with 20 g (0.15 mol) of dimethyl 
malonate and 9.7 g (0.18 mol) of NaOMe in methanol at room temperature for 
four hours to obtain 14.4 g of 
3-methoxy-carbonyl-2H-cyclohepta(b)furan-2-one (compound (2)). To 12 g of 
the compound (2) were added 200 ml of acetone and 70 ml of diethylamine, 
and the mixture was refluxed for 30 hours. Water was added to this 
mixture, and the resulting mixture was extracted with toluene to obtain 
39.2 g of methyl-2-methyl-azulenecarboxylate. To this compound was further 
added 25 ml of phosphoric acid, and reaction was carried out at a 
temperature of 85 to 90.degree. C. for one hour. The reaction mixture was 
subjected to decomposition with water, and the resultant was extracted 
with benzene. The organic phase was dried to obtain 6.5 g of the desired 
compound, 2-methylazulene. 
A solution (26.7 ml, 1.0 mole/liter) of methyllithium in ether was added 
dropwise to a solution of the 2-methylazulene (3.44 g, 24 mmol) in THF (50 
ml) at 0.degree. C. The mixture was stirred at 0.degree. C. for 10 minutes 
and at room temperature for 10 minutes, and then cooled to -78.degree. C. 
To this mixture was added a solution of dichlorodimethylsilane (1.76 ml, 
14.5 mol) in THF (5 ml). The mixture was stirred at -78.degree. C. for 30 
minutes and at room temperature for 1.5 hours, and then heated at 
50.degree. C. for 2 hours. The mixture was treated with water, and 
subjected to separation using a silica gel column (hexane:methylene 
chloride=20:1), whereby a colorless and transparent oily compound, 
bis[1-(2,4-dimethyl-1,4-dihydroazulenyl)]dimethylsilane (compound (3)) 
(1.44 g, 32%), was obtained as a mixture of 8 types of diastereomers. 
Subsequently, in diethyl ether, 4.74 ml (7.73 mmol) of a solution of 
n-butyl lithium (1.63 mol/liter) in n-hexane was added dropwise to 1.33 g 
of the above-synthesized compound (3) at a temperature of -50.degree. C. 
or lower over a period of 30 minutes. The temperature of the mixture was 
gradually raised to room temperature, and the mixture was then stirred for 
one hour. The solvent was distilled off, and the residue was cooled to 
-70.degree. C. Cold methylene chloride was added to the residue, and 
zirconium tetrachloride was then introduced to the mixture over a period 
of 3 minutes. The mixture was maintained at the temperature for one hour. 
After the temperature of the mixture was raised to room temperature, the 
mixture was stirred for an additional 10 hours. Subsequently, the solid 
was separated by filtration, and the filtrate was distilled off. The 
residue was recrystallized from a mixture of toluene and n-hexane to 
obtain 1.2 g of a dark green solid. From the results of .sup.1 HNMR 
analysis, the solid was identified as 
dimethyl-silylenebis(2,4-dimethyl-4-hydroazulenyl)zirconium dichloride 
(compound (4)). 
0.25 g (0.47 mmol) of the compound (4) was dissolved in 35 ml of methylene 
chloride, and the solution was introduced, along with 30 mg of platinum 
dioxide, into a 0.1-liter autoclave. The mixture was stirred at room 
temperature under a hydrogen pressure of 40 bar for 4 hours. After 
hydrogen was purged, the solution phase was separated by filtration, 
dried, and then dissolved in toluene. n-Pentane was added to the solution. 
The precipitate was separated by filtration, and dried to obtain 0.11 g of 
a light-yellow-greenish white solid. It was confirmed by .sup.1 HNMR 
analysis that this solid was the desired compound. 
&lt;Polymerization of Propylene&gt; 
The inside of a 1.5-liter autoclave equipped with a stirring means was 
thoroughly replaced with propylene. 500 ml of thoroughly dehydrated and 
deoxygenated toluene was introduced into the autoclave, followed by the 
introduction of 10 mmol (0.58 g) (on the basis of Al atom) of "MMAO" 
(modified MAO) manufactured by TOSO-AKZO CORPORATION, and 0.54 mg (1 
micromol) of the above-synthesized 
dimethylsilylenebis(2,4-dimethyl-hexahydro-azulenyl)zirconium dichloride. 
To this was introduced propylene, and preliminary polymerization was 
carried out at 20.degree. C. under 1 kg/cm.sup.2 G for 15 minutes. The 
temperature of the mixture was then raised to 40.degree. C., and 
polymerization was carried out under 7 kg/cm.sup.2 G for 2 hours. After 
the polymerization was completed, the polymer slurry obtained was filtered 
to separate the solid produced. The solid was dried to obtain 79.0 g of a 
polymer. The catalytic activity was 14.6.times.10.sup.4 
g-polymer/g-Component (A). The number-average molecular weight (Mn), the 
distribution of molecular weight (Mw/Mn) and the melting point of the 
polymer were found to be 6.06.times.10.sup.4, 2.30, and 148.4.degree. C., 
respectively. 
EXAMPLE 2 
&lt;Polymerization of Propylene&gt; 
Propylene was polymerized under the same conditions as in Example 1 except 
that the polymerization temperature was changed to 70.degree. C. The 
results obtained are as shown in Table 1. 
EXAMPLE 3 
&lt;Polymerization of Propylene&gt; 
Propylene was polymerized under the same conditions as in Example 1 except 
that 1 mmol (0.198 g) (on the basis of Al atom) triisobutylaluminum and 
0.80 mg (1 micromol) of N,N-dimethylanilinium 
tetrakispentafluorophenylborate were used instead of the 
methylisobutylalumoxane used in Example 1. The results obtained are as 
shown in Table 1. 
EXAMPLE 4 
&lt;Synthesis of 
dimethylsilylenebis(2,4-dimethyl-4,5,6,7-tetra-hydroindenyl)zirconium 
dichloride&gt; 
In a 500-ml glass-made reactor, 4.76 g (33 mmol) of 2,4-dimethylindene was 
dissolved in 80 ml of tetrahydrofuran, and the solution was cooled to no 
higher than -50.degree. C. 21 ml of a 1.6 M solution of n-butyl lithium in 
hexane was slowly added dropwise into the reactor. The mixture was stirred 
at room temperature for one hour, and then cooled again to -20.degree. C. 
To this was slowly added dropwise 2.1 g of dimethyldichlorosilane, and the 
mixture was stirred at room temperature for 12 hours. 50 ml of water was 
then added to the mixture. The organic phase was separated, and dried to 
obtain 3.8 g of dimethylbis(2,4-dimethylindenyl)silane. 
3.5 g of the above-obtained dimethylbis(2,4-dimethyl-indenyl)silane was 
dissolved in 70 ml of tetrahydrofuran. To this solution was slowly added 
dropwise a 1.6 M solution of n-butyl lithium in hexane with cooling. After 
the mixture was stirred at room temperature for 3 hours, it was slowly 
added dropwise to a solution of zirconium tetrachloride (2.6 g, 11 mmol) 
in tetrahydrofuran (60 ml). After the resulting mixture was stirred for 5 
hours, hydrogen chloride gas was blown into the mixture, and the mixture 
was then dried. Subsequently, methylene chloride was added to the mixture, 
and the soluble matter was separated and crystallized at a low temperature 
to obtain 0.45 g of an orange powder. 
It was confirmed by a .sup.1 HNMR analysis that the compound obtained was 
dimethylsilylenebis (2,4-dimethylindenyl)zirconium dichloride (compound 
(5)) and that the two 2,4-dimethylindenyl groups in the compound were 
asymmetric. 
0.50 g (0.99 mmol) of the compound (5) was dissolved in 35 ml of methylene 
chloride. The solution was introduced, along with 50 mg of platinum 
dioxide, into a 0.1-liter autoclave, and reaction was carried out at 
70.degree. C. under a hydrogen pressure of 40 bar for 6 hours. After the 
reaction mixture was cooled to room temperature, hydrogen was purged. The 
solution phase was separated by filtration, and dried. The residue was 
dissolved in toluene, and n-pentane was added to the solution. The solid 
precipitated was separated by filtration, and dried to obtain 0.15 g of a 
light-greenish white solid. It was confirmed by .sup.1 HNMR analysis that 
the solid obtained was the desired compound. 
&lt;Polymerization of Propylene&gt; 
Propylene was polymerized under the same conditions as in Example 1 except 
that dimethylsilylenebis(2,4-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium 
dichloride was used instead of the 
dimethylsilylenebis(2,4-dimethyl-hexahydroazulenyl)-zirconium dichloride 
used in Example 1. 
As a result, 120.8 g of a polymer was obtained. The catalytic activity was 
23.6.times.10.sup.4 g-polymer/g-Component (A). The number-average 
molecular weight (Mn), the distribution of molecular weight (Mw/Mn) and 
the melting point of the polymer were found to be 17.3.times.10.sup.4, 
2.45, and 148.2.degree. C., respectively. 
EXAMPLE 5 
&lt;Polymerization of Propylene&gt; 
Propylene was polymerized under the same conditions as in Example 4 except 
that the polymerization temperature was changed to 70.degree. C. The 
results obtained are as shown in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Melting 
Number-Average 
Polymerization 
Catalytic Activity 
Point 
Molecular 
Mw/Mnt 
Complex Component (B) 
Component (B) 
temperature 
(g/g-Component A)) 
(.degree. C.) 
(Mn) (= Q) 
__________________________________________________________________________ 
Example 1 
(1) MMAO -- 40.degree. C. 
148,000 148.4 
60,600 2.30 
1 .mu.M 
10 mM 
Example 2 
(1) .dwnarw. 
-- 70.degree. C. 
294,000 144.8 
45,500 2.25 
1 .mu.M 
Example 3 
(1) triisobutyl- 
dimethylanilinium 
40.degree. C. 
125,500 148.8 
51,800 2.35 
1 .mu.M 
aluminum 
tetrakispentafluoro- 
phenylborate 
1 .mu.M 
Example 4 
(2) MMAO -- 40.degree. C. 
236,000 148.2 
173,000 2.45 
1 .mu.M 
10 mM 
Example 5 
(2) .dwnarw. 
-- 70.degree. C. 
432,000 146.3 
131,000 2.38 
1 .mu.M 
__________________________________________________________________________ 
(1) Dimethylsilylenebis(2,4dimethyl-hexahydroazulenyl)zirconium dichlorid 
(2) Dimethylsilylenebis(2,4dimethyl-4,5,6,7-tetrahydroindenyl)zirconium 
dichloride 
EXAMPLE 6 
Synthesis of Ethylenebis(2,4,4-trimethyl-hexahydroazulenyl)-zirconium 
dichloride 
Ethylenebis(2,4,4-trimethyl-hexahydroazulenyl)-zirconium dichloride was 
synthesized in accordance with the Scheme 1 attached herein below, where 
the compound is numbered (19). 2,2-Dimethylcycloheptanone (13) was 
synthesized in accordance with the method described in the pertinent 
reference set forth in the Scheme 1. 
In the syntheses which follow, the numeral in parentheses means the 
compound indicated by the numeral in the Scheme 1. 
Synthesis of Propargylcycloheptanone (14) 
A solution of lithium diisopropylamide (LDA) in THF (50 ml) was added to a 
solution of 2,2-dimethylcycloheptanone (13) (10.55 g, 75.37 mmol) in THF 
(30 ml) at a temperature of 0.degree. C. The mixture was stirred at room 
temperature for one hour. To this was added dropwise propargylbromide 
(6.85 ml, 90.44 mmol) at 0.degree. C. The mixture was stirred at room 
temperature for one hour, and then heated at 50.degree. C. for 3 hours. 
The mixture was treated with an aqueous ammonium chloride solution, and 
then purified by distillation (100.degree. C., 2 mmHg) to obtain 
propargyl-cycloheptanone (14) (7.34 g, 55%). 
.sup.1 HNMR (300 MHz, CDCl.sub.3) .delta. 1.36 (s, 6H, (CH.sub.3).sub.2), 
1.1-2.20 (m, 9H), 2.40-2.52 (m, 1H), 2.70-2.84 (m, 1H), 3.30-3.41 (m, 1H); 
EI-MS m/z 178 (20, M.sup.+), 135 (50), 79 (70), 69 (100), 41 (87) 
Synthesis of Acetonylcycloheptanone (15) 
Mercury oxide (116 mg) was dissolved in water (10 ml). To this solution 
were added concentrated sulfuric acid (0.5 ml) and methanol (10 ml). To 
this solution, a solution of the propargylcycloheptanone (14) (7.34 g, 
41.23 mmol) in methanol (20 ml) was added little by little, and the 
mixture was heated at 60.degree. C. for 20 minutes. After the mixture was 
cooled, sodium chloride was dissolved in the mixture. The solution was 
extracted with a mixture of hexane and ether to obtain 
acetonylcycloheptanone (15) (8.26 g, quant.). 
.sup.1 HNMR (300 MHz, CDCl.sub.3) .delta. 1.08 (s, 3H, CH.sub.3), 1.16 (s, 
3H, CH.sub.3), 1.05-1.85 (m, 8H, CH.sub.2), 2.12 (s, 3H, CH.sub.3 CO), 
2.29 (dd, .sup.3 J=18 Hz, .sup.2 J=4 Hz, 1H), 3.11 (dd, .sup.3 J=18 Hz, 
.sup.3 J=10 Hz, 1H), 3.40-3.41 (m, 1H); .sup.13 CNMR (75 MHz, CDCl.sub.3) 
.delta. 23.48 (CH.sub.3), 24.33, 28.48 (CH.sub.3), 29.77, 30.14 (CH.sub.3 
CO), 32.97, 38.70, 43.00 (CH), 46.55 (CHCH.sub.2), 47.62((CH.sub.3).sub.2 
C), 207.49 (CO), 218.39 (CO); EI-MS m/z 196 (2, M.sup.+), 163 (26), 140 
(13), 43 (100, CH.sub.3 CO.sup.+) 
Synthesis of Enone (16) 
The acetonylcycloheptanone (15) (7.0 g, 35.7 mmol) was added to a solution 
of sodium hydride (2.8 g, 60% content, 71.4 mmol) in toluene (300 ml), and 
the solution was refluxed by heating for 2.5 hours. After the solution was 
cooled, ethanol was added to the solution little by little, and allowed to 
react with the excessive sodium hydride. Subsequently, the solution was 
neutralized with dilute hydrochloric acid. The crude product obtained was 
purified by column chromatography (SiO.sub.2, hexane:AcOEt=3:1) to obtain 
enone (16) (4.1 g, 65%). 
.sup.1 HNMR (300 MHz, CDCl.sub.3) .delta. 0.74 (s, 3H, CH.sub.3), 1.00 (s, 
3H, CH.sub.3), 1.40-1.90 (m, 8H, CH.sub.2), 2.25-2.30 (m, 1H), 2.39-2.50 
(m, 1H), 2.90-2.99 (m, 1H), 5.95 (brs, 1H, CH.dbd.); EI-MS m/z 178 (7, 
M.sup.+), 136 (100), 121 (46), 107 (24) 
Synthesis of 2,4,4-Trimethylhexahydroazulene (17) 
A solution of methyl lithium (27.64 mmol) in ether was added to a solution 
of the enone (4.1 g, 23.03 mmol) in THF (40 ml) at 0.degree. C., and the 
mixture was stirred overnight at room temperature. To this was added an 
aqueous ammonium chloride solution, and dilute hydrochloric acid was then 
further added to the mixture to acidify the aqueous layer. By this, 
dehydration was proceeded, and the crude product, the compound (17), was 
obtained. The product was purified by column chromatography (SiO.sub.2, 
hexane) to obtain 2,4,4-trimethylhexa-hydroazulene (17) (2.86 g, 71%). 
.sup.1 HNMPR (300 MHz, CDCl.sub.3) .delta. 1.38 (s, 3H, (CH.sub.3).sub.2), 
1.75-1.90 (m, 4H), 1.95-2.10 (m, 2H), 2.23 (s, 3H, CH.sub.3 C.dbd.), 
2.60-2.68 (m, 2H), 3.08 (s, 2H, CH.sub.2), 6.36 (brs, 1H, CH.dbd.); EI-MS 
m/z 176 (30, M.sup.+), 161 (100, M.sup.+ -Me), 119 (43), 105 (15) 
Synthesis of Crosslinked Compound (18) 
A solution of dibutyl magnesium (0.85 mmol) in heptane was added to a 
solution of the 2,4,4-trimethylhexahydroazulene (298 mg, 1.69 mol) in 
toluene (5 ml) at room temperature. The mixture was stirred at room 
temperature for one hour and at 100.degree. C. for 2.5 hours, and then 
cooled to 0.degree. C. To this were added THF (5 ml) and dibromoethane (72 
microliter, 0.85 mmol). The mixture was stirred at room temperature for 3 
hours and at 50.degree. C. for one hour. The mixture was then treated with 
an aqueous ammonium chloride solution, and purified by column 
chromatography to obtain crosslinked compound (18). 
Synthesis of Ethylenebis(2,4,4-Trimethylhexahydroazulenyl)-zirconium 
dichloride (19) 
0.12 g of the crosslinked compound (18) was dissolved in diethyl ether. To 
this solution was added dropwise 0.39 ml (0.63 mmol) of a solution of 
n-butyl lithium (1.63 mol/liter) in n-hexane at a temperature of no hither 
than -50.degree. C. The temperature of the mixture was gradually raised to 
room temperature. The mixture was stirred for one hour, and then cooled 
again to no higher than -50.degree. C. To this was added 0.12 g of 
zirconium tetrachloride/diethyl ether complex compound (containing two 
diethyl ether molecules per zirconium atom). After the addition was 
completed, the temperature of the mixture was gradually raised to room 
temperature, and the mixture was stirred for 20 hours. 
The reaction mixture was concentrated under reduced pressure, and extracted 
with toluene. The organic phase was concentrated, and n-hexane was further 
added thereto. The mixture was cooled, and the solid was separated and 
dried. The yield was 0.05 g. It was confirmed by a .sup.1 HNMR analysis 
that the solid obtained was 
ethylenebis(2,4,4-trimethylhexahydro-azulenyl)zirconium dichloride (19). 
##STR6## 
References 6-10: Wallach, O.; Mallison, H.: Justus Liebigs Ann. Chem. 
1908, 360, 68. 
10-13: Sisui, A. J.; Meyers, M.: J. Org. Chem. 1973, 26, 4431 
EXAMPLE 7 
Synthesis of 
Dimethylsilylenebis(2-methyl-3,4,5,6,7,8-hexahydro-4-phenylazulenyl)zircon 
ium dichloride&gt; 
Synthesis of dimethylbis[1-(2-methyl-4-phenyl-1,4-dihydroazulenyl)]silane 
(2) 
The syntheses followed Scheme 2 appended hereto, and the compounds numbered 
herein are those indicated in Scheme 2. 
2-Methylazulene (1) (2.22 g, 15.66 mmol) was dissolved in hexane (30 mL), 
to which was added a solution of phenyllithium in cyclohexane-ether (15.6 
mL, 1.0 mole/liter) gradually at 0.degree. C. The solution was stirred for 
1 hour at room temperature, followed by cooling to -78.degree. C. and then 
addition of tetrahydrofuran (30 mL). To this was added 
dimethyldichlorosilane (0.95 mL, 7.83 mmol) and the mass was warmed to 
room temperature and then heated to 50-60.degree. C. for 1.5 hrs. Aqueous 
ammonium chloride was then added, and the organic layer formed was 
separated, dried over magnesium sulfate, and the solvent was then 
evaporated in vacuo. The crude product obtained gave, upon purification by 
silica gel chromatography, 
dimethylbis[1-(2-methyl-4-phenyl-1,4-dihydroazulenyl)]silane (1.48 g, 
38%). 
.sup.1 HNMR (300 MHz, CDCl.sub.3) .delta. 0.63-0.00 (m, 6H, 
Si(CH.sub.3).sub.2), 2.0-2.1 (m, 6H, CH.sub.3), 3.55-3.93 (m, 4H), 
5.45-5.87 (m, 4H), 6.05-6.30 (m, 4H), 6.55-6.80 (m, 2H), 7.15-7.55 (m, 
10H). 
Synthesis of 
dimethylsilylenebis(2-methyl-4-hydro-4-phenylazulenyl)zirconium dichloride 
(3) 
All of the following procedures were carried out under the nitrogen 
atmosphere, and the solvents used were the ones which had been thoroughly 
desiccated and deoxygenated. 
To a solution of the thus synthesized compound (2) (0.768 g, 1.55 mmol) 
dissolved in diethylether (15 ml) was added at -76.degree. C. dropwise a 
1.98 ml of a solution of n-butyllithium in hexane, and the solution was 
raised gradually to room temperature at which a reaction took place for 12 
hours. The solvent was then distilled off in vacuo, the product remained 
was washed with hexane and the hexane was again distilled off. To the 
product obtained was added 20 ml of a mixture of toluene/diethylether of 
40/1, followed by addition at -60.degree. C. of zirconium tetrachloride 
(0.325 g, 1.40 mmol). The admixture formed was warmed gradually to room 
temperature at which a reaction took place for 15 hours. After the 
reaction, the product was filtered, the solid product obtained was 
extracted with toluene, and the extract was concentrated. To the extract 
concentrated was added hexane to form a precipitate, which was then 
recrystallized to give a brownish yellow solid product (0.15 g). The solid 
product was formed, upon .sup.1 HNMR analysis, to be a 50/50 mixture of 
the racemic product and the meso product of 
dimethylsilylenebis(2-methyl-4-hydro-4-phenylazulenyl)-zirconium 
dichloride (3). 
The product (3) obtained (70 mg, 0.11 mmol) dissolved in 10 ml of methylene 
chloride was added to a 0.1-liter autoclave and platinum oxide (10 mg, 
0.04 mmol) in methylene chloride (10 ml) was also added. The autoclave was 
agitated for 5 hours under a hydrogen pressure of 40 kg/cm.sup.2, and the 
product was then filtered to give 
dimethylsilylenebis(2-methyl-3,4,5,6,7,8-hexahydro-4-phenylazulenyl)zircon 
ium dichloride (4) as an orange yellow solid (20 mg). 
##STR7## 
EXAMPLE 8 
&lt;Polymerization of propylene&gt; 
After a 1.5-liter autoclave equipped with a stirring means had been 
thoroughly purged with propylene, toluene (500 ml) which had been 
desiccated and deoxygenated thoroughly was introduced, followed by "PMAO" 
(methyl-alumoxane, manufactured by Toso-Akzo Japan, polymerization degree: 
16) in an amount of 1.5 mmole (0.087 g) based on Al atom. 
The autoclave was warmed to 40.degree. C., and 
dimethylsilylenebis(2-methyl-3,4,5,6,7,8-hexahydro-4-phenylazulenyl)zircon 
ium dichloride (4) (0.100 mg, 0.15 pmol) was introduced followed by 
addition of 100 ml of hydrogen. Polymerization took place upon 
introduction of propylene at a pressure of 7 kg/cm.sup.2 G for 1.5 hours. 
The polymer slurry thus formed was filtered, and the polymer was obtained 
upon drying in an amount of 37.0 g. 
The catalyst activity was 185,000 g of polymer/g of complexehour, and the 
polymer thus obtained a number average molecular weight (Mn) of 
3.24.times.104, a molecular weight distribution (Mw/Mn) of 3.34 and a 
melting point of 158.9.degree. C. 
EXAMPLE 9 
&lt;Polymerization of propylene&gt; 
Propylene was polymerized in the same manner as in Example 8 except that 
polymerization was carried out at a temperature of 70.degree. C. 
The catalyst activity was 211,000 g of polymer/g of the complex.hour, and 
the polymer thus obtained had a number average molecular weight (Mn) of 
3.96.times.10.sup.4, a molecular weight distribution (Mw/Mn) of 4.37, and 
a melting point of 157.1.degree. C. 
EXAMPLE 10 
&lt;Polymerization of propylene&gt; 
Propylene was polymerized in the same manner as in Example 9 except that 
polymerization was carried out in the absence of hydrogen added. 
The catalyst activity was 82,000 g of polymer/g of the complexohour, and 
the polymer thus obtained had a number average molecular weight (Mn) of 
19.6.times.10.sup.4, a molecular weight distribution (Mw/Mn) of 2.98, and 
a melting point of 154.9.degree. C.