Crosslinked metallocene compound for olefin polymerization and method of polymerizing olefin with the same Number:7,393,965 from the United States Patent and Trademark Office (PTO) owispatent

Title: Crosslinked metallocene compound for olefin polymerization and method of polymerizing olefin with the same

Abstract: The bridged metallocene compound or the olefin polymerization catalyst which comprises the compound, enables high polymerization activity in polymerizing one or more monomers selected from ethylene and .alpha.-olefins. The bridged metallocene compound contains specific substituted cyclopentadienyl and fluorenyl groups which are linked via carbon or silicon atoms. In the method for the preparation of polyolefins, one or more monomers, preferably ethylene as an essential monomer, selected from ethylene and .alpha.-olefins are copolymerized in the presence of the olefin polymerization catalyst comprising the bridged metallocene compound, so that an ethylene based polymer with an ethylene content of more than 50 mol % is obtained.

Patent Number: 7,393,965 Issued on 07/01/2008 to Tohi,   et al.

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Inventors:	Tohi; Yasushi (Sodegaura, JP), Endo; Koji (Sodegaura, JP), Kaneyoshi; Hiromu (Sodegaura, JP), Urakawa; Naomi (Sodegaura, JP), Yamamura; Yuichi (Sodegaura, JP), Kawai; Koji (Sodegaura, JP)
Assignee:	Mitsui Chemicals, Inc. (Tokyo, JP)
Appl. No.:	10/529,461
Filed:	February 17, 2003
PCT Filed:	February 17, 2003
PCT No.:	PCT/JP03/01656
371(c)(1),(2),(4) Date:	October 28, 2005
PCT Pub. No.:	WO2004/029062
PCT Pub. Date:	April 08, 2004

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Foreign Application Priority Data

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Sep 27, 2002 [JP]			2002-283291
Nov 22, 2002 [JP]			2002-339670

Current U.S. Class:	556/11 ; 502/103; 502/117; 526/160; 526/943; 556/12
Current International Class:	C07F 17/00 (20060101); B01J 31/00 (20060101); C07F 7/00 (20060101)
Field of Search:	556/11,12 502/103,117 526/160,943

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References Cited [Referenced By]

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U.S. Patent Documents

5886202	March 1999	Jung
6469188	October 2002	Miller et al.
2002/0137959	September 2002	Rix

Foreign Patent Documents

	1328580		Dec., 2001		CN
	5 775 81		Jan., 1994		EP
	6 854 95		Dec., 1995		EP
	1 138 687		Oct., 2001		EP
	2-41303		Feb., 1990		JP
	2-78687		Mar., 1990		JP
	2-167305		Jun., 1990		JP
	2-274703		Nov., 1990		JP
	3-103407		Apr., 1991		JP
	3-193797		Aug., 1991		JP
	4-69394		Mar., 1992		JP
	05-059077		Mar., 1993		JP
	5-125112		May., 1993		JP
	6-172443		Jun., 1994		JP
	07-157508		Jun., 1995		JP
	2000-26490		Jan., 2000		JP
	2000-212194		Aug., 2000		JP
	WO-00/24793		May., 2000		WO
	WO-01/27124		Apr., 2001		WO

Other References

Kaminsky et al., Angew. Chem. Int. Ed. Engl., 24, 507-508 (1985). cited by other . Ewen et al., J. Amer. Chem. Soc., 110, 6255-6256 (1988). cited by other . Kaminsky et al., Makromol. Chem. 193, 1643-1651 (1992). cited by other . Chen et al., Journal of Organometallic Chemistry 497 (1995) pp. 1-9. cited by other . Patsidis et al., Journal of Organometallic Chemistry 509 (1996) pp. 63-71. cited by other.

Primary Examiner: Gonzale; Porfirio Nazario
Attorney, Agent or Firm: Birch, Stewart, Kolasch & Birch, LLP

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Claims

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The invention claimed is:

1. A bridged metallocene compound represented by the formula [I]: ##STR00022## wherein Y is a carbon, silicon, germanium or tin atom; M is Ti or Zr; R.sup.1 to R.sup.12, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group; neighboring substituents of R.sup.5 to R.sup.12 may be linked with each other to form a ring; R.sup.13 and R.sup.14 are unsubstituted or substituted aryl groups, at least one of which is a substituted aryl group; Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural; and j is an integer from 1 to 4.

2. The bridged metallocene compound of the formula [I] as claimed in claim 1, wherein R.sup.13 or R.sup.14 is a substituted aryl group which has one or more substituents of the same or different kind selected from hydrocarbon groups of 1 to 20 carbon atoms, halogen-containing hydrocarbon groups, halogen atoms, oxygen-containing groups and nitrogen-containing groups.

3. A bridged metallocene compound represented by the formula [I]: ##STR00023## wherein Y is a carbon, silicon, germanium or tin atom; M is Ti, Zr or Hf; R.sup.1 to R.sup.12, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group; neighboring substituents of R.sup.5 to R.sup.12 may be linked with each other to form a ring; either or both of R.sup.13 and R.sup.14 is represented by R.sup.15R.sup.16CH--, in which R.sup.15 and R.sup.16 are each hydrogen, a hydrocarbon group or a silicon-containing group; and when one of R.sup.13 and R.sup.14 is not as defined above, then R.sup.13 or R.sup.14 is a hydrocarbon group or a silicon-containing group and may be linked with each other to form a ring (when R.sup.5 to R.sup.12 are all hydrogen or when R.sup.6 and R.sup.11 are both hydrocarbon groups, R.sup.13 and R.sup.14 are hydrocarbon groups other than phenyl, methyl and polymethylene groups, and when R.sup.7 and R.sup.10 are both hydrocarbon groups, R.sup.13 and R.sup.14 are hydrocarbon groups other than phenyl and methyl groups); Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural; and j is an integer from 1 to 4.

4. The bridged metallocene compound of the formula [I] as claimed in claim 3, wherein either or both of R.sup.13 and R.sup.14 is represented by R.sup.15R.sup.16CH--, in which R.sup.15 and R.sup.16 are linked with each other to form a ring.

5. A bridged metallocene compound represented by the formula [I]: ##STR00024## wherein Y is a carbon atom; M is Ti, Zr or Hf; R.sup.1 to R.sup.12, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group; neighboring substituents of R.sup.5 to R.sup.12 may be linked with each other to form a ring; R.sup.13 and R.sup.14 are linked with each other to form a polymethylene group represented by --CH.sub.2(CH.sub.2).sub.n--, in which n is an integer from 1 to 10; and R.sup.7 and R.sup.10 are hydrocarbon groups of 1 to 20 carbon atoms; Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural; and j is an integer from 1 to 4.

6. A bridged metallocene compound represented by the formula [I]: ##STR00025## wherein Y is a carbon, silicon, germanium or tin atom; M is Ti, Zr or Hf; R.sup.1 to R.sup.12, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group, wherein arbitrary three or more substituents of R.sup.5 to R.sup.12 are hydrocarbon groups of 1 to 20 carbon atoms or silicon-containing groups; R.sup.13 and R.sup.14, which may be the same or different, are each a hydrocarbon group or a silicon-containing group and may be linked with each other to form a ring (when R.sup.6 and R.sup.11 are both hydrocarbon groups, R.sup.13 and R.sup.14 are hydrocarbon groups other than phenyl, methyl and polymethylene groups and when R.sup.7 and R.sup.10 are both hydrocarbon groups, R.sup.13 and R.sup.14 are hydrocarbon groups other than phenyl and methyl groups); Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural; and j is an integer from 1 to 4.

7. The bridged metallocene compound of the formula [I] as claimed in claim 6, wherein R.sup.6, R.sup.7, R.sup.10 and R.sup.11 are hydrocarbon groups of 1 to 20 carbon atoms or silicon-containing groups.

8. The bridged metallocene compound of the formula [I] as claimed in claim 6, wherein R.sup.6 and R.sup.7, and R.sup.10 and R.sup.11 are linked with each other to form rings.

9. A bridged metallocene compound represented by the formula [I]: ##STR00026## wherein Y is a silicon, germanium or tin atom; M is Ti, Zr or Hf; R.sup.1 to R.sup.12, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group, wherein R.sup.5 to R.sup.12 are not hydrogen at the same time; neighboring substituents of R.sup.5 to R.sup.12 may be linked with each other to form a ring; R.sup.13 and R.sup.14, which may be the same or different, are each a hydrocarbon group or a silicon-containing group and may be linked with each other to form a ring (when R.sup.6 and R.sup.11 are both hydrocarbon groups, R.sup.13 and R.sup.14 are hydrocarbon groups other than phenyl, methyl and polymethylene groups; when R.sup.7 and R.sup.10 are both hydrocarbon groups, R.sup.13 and R.sup.14 are hydrocarbon groups other than phenyl and methyl groups; and where R.sup.6 and R.sup.11 are not t-butyl groups when R.sup.13 and R.sup.14 are methyl or phenyl groups); Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural; and j is an integer from 1 to 4.

10. The bridged metallocene compound of the formula [I] as claimed in claim 9, wherein Y is a silicon or germanium atom.

11. The bridged metallocene compound of the formula [I] as claimed in claim 1, wherein R.sup.1 to R.sup.4 are all hydrogen.

12. An olefin polymerization catalyst comprising the bridged metallocene compound of claim 1.

13. An olefin polymerization catalyst comprising: (A) the bridged metallocene compound of claim 1 and (B) at least one compound selected from: (B-1) an organometallic compound, (B-2) an organoaluminum oxy-compound and (B-3) a compound which reacts with the metallocene compound (A) to form an ion pair.

14. A method for olefin polymerization, in which one or more monomers, essentially ethylene, selected from ethylene and .alpha.-olefins are polymerized in the presence of the olefin polymerization catalyst of claim 13 that an ethylene based polymer with an ethylene content of more than 50 mol % is obtained.

15. A method for olefin polymerization, in which one or more monomers, essentially ethylene, selected from ethylene and .alpha.-olefins are polymerized in the presence of an olefin polymerization catalyst which comprises a bridged metallocene compound of the formula [I'] so that an ethylene based polymer with an ethylene content of more than 50 mol % is obtained: ##STR00027## wherein Y is a carbon, silicon, germanium or tin atom; M is Ti, Zr or Hf; R.sup.1 to R.sup.12, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group; R.sup.5 to R.sup.12 are not hydrogen at the same time; neighboring substituents of R.sup.5 R.sup.12 may be linked with each other to form a ring; R.sup.13 and R.sup.14, which may be the same or different, are each a hydrocarbon group or a silicon-containing group and may be linked with each other to form a ring; Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural; and j is an integer from 1 to 4.

16. The method for olefin polymerization as claimed in claim 14, wherein the metallocene compound of the formula [I] or [I'] has been supported on a carner.

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Description

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FIELD OF THE INVENTION

The present invention relates to a bridged metallocene compound of specific structure useful as a catalyst or a catalyst component for polymerization of olefins, and to a method for polymerization of one or more monomers selected from ethylene and .alpha.-olefins in the presence of a catalyst containing the bridged metallocene compound.

BACKGROUND OF THE INVENTION

Metallocene compounds are well known as homogeneous catalysts for polymerization of olefins. Polymerization of olefins using these metallocene compounds, particularly stereoregular polymerization of .alpha.-olefins, has improved much since the report of isotactic polymerization by W. Kaminsky et al. (Angew. Chem. Int. Ed. Engl., 24, 507 (1985)), but further improvement has been required in terms of polymerization activity and stereoregularity. As part of studies for the improvement, propylene polymerization using a metallocene compound in which a cyclopentadienyl ligand and a fluorenyl ligand are bridged, has been reported by J. A. Ewen (J. Am. Chem. Soc., 110, 6255 (1988)). Further, W. Kaminsky has reported ethylene polymerization using the same catalyst (Makromol. Chem., 193, 1643 (1992)).

However, polymerization of ethylene as a major monomer has suffered insufficient polymerization activity, so that a transition metal compound capable of enhanced polymerization activity or a polymerization catalyst comprising the transition metal compound has been demanded.

DISCLOSURE OF THE INVENTION

A bridged metallocene compound (W) of the invention (sometimes referred to as a "metallocene compound" hereinafter) is represented by the formula [I]:

##STR00001## wherein Y is a carbon, silicon, germanium or tin atom; M is Ti, Zr or Hf, R.sup.1 to R.sup.12, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group; neighboring substituents of R.sup.5 to R.sup.12 may be linked with each other to form a ring; R.sup.13 and R.sup.14, which may be the same or different, are each a hydrocarbon group or a silicon containing group and may be linked with each other to form a ring (when R.sup.5 to R.sup.12 are all hydrogen or when R.sup.6 and R.sup.11 are both hydrocarbon groups, R.sup.13 and R.sup.14 are hydrocarbon groups other than phenyl, methyl and pentamethylene groups, and when R.sup.7 and R.sup.10 are both hydrocarbon groups, R.sup.13 and R.sup.14 are hydrocarbon groups other than phenyl and methyl groups); Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural; and j is an integer from 1 to 4.

The metallocene compound (W) of the formula [I] can be classified into five types (W-1) to (W-5) by the chemical structure. These preferable metallocene compounds (W-1) to (W-5) are represented by the formula [I-1] to [I-5] respectively. When the metallocene compound has plural characteristic structures, it will be represented by corresponding plural formulae of [I-1] to [I-5].

##STR00002##

In the formula [I-1], R.sup.1 to R.sup.12, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group; neighboring substituents of R.sup.1 to R.sup.12 may be linked with each other to form a ring; M is Ti or Zr; Y is a Group 14 atom; Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural; j is an integer from 1 to 4; R.sup.13 is an unsubstituted or substituted aryl group, R.sup.14 is a substituted aryl group, and R.sup.13 and R.sup.14 may the same or different when R.sup.13 is a substituted aryl group.

##STR00003##

In the formula [I-2], R.sup.1 to R.sup.16, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group; neighboring substituents of R.sup.1 to R.sup.12 may be linked with each other to form a ring; R.sup.13 to R.sup.16 cannot be hydrogen at the same time; R.sup.13 and R.sup.14 may be linked with each other to form a ring; R.sup.15 and R.sup.16 may be linked with each other to form a ring; M is Ti, Zr or Hf; Y is a carbon atom; Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural; and j is an integer from 1 to 4.

##STR00004##

In the formula [I-3], R.sup.1 and R.sup.2, which may be the same or different, are each hydrogen, a hydrocarbon group, a silicon-containing group or a halogen-containing group; M is Ti, Zr or Hf; Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural; n is an integer from 1 to 10; and j is an integer from 1 to 4.

##STR00005##

In the formula [I-4], R.sup.1 to R.sup.14, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group; arbitrary three or more groups of R.sup.6, R.sup.7, R.sup.10 and R.sup.11 cannot be hydrogen at the same time; neighboring substituents of R.sup.5 to R.sup.12 may be linked with each other to form a ring; R.sup.13 and R.sup.14, which may be the same or different, are each a hydrocarbon group or a silicon-containing group and may be linked with each other to form a ring; Y is a carbon atom; M is Ti, Zr or Hf; Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural; and j is an integer from 1 to 4.

##STR00006##

In the formula [I-5], R.sup.1 to R.sup.12, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group but cannot be hydrogen at the same time; neighboring substituents of R.sup.1 to R.sup.12 may be linked with each other to form a ring; Y is a silicon, germanium or tin atom; R.sup.13 and R.sup.14, which may be the same or different, are each a hydrocarbon group or a silicon-containing group and may be linkedwitheachother to forma ring; R.sup.6and R.sup.11 cannot be t-butyl groups when R.sup.13 and R.sup.14 are both methyl or phenyl groups; M is Ti, Zr or Hf; Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural; and j is an integer from 1 to 4.

An olefin polymerization catalyst of the invention comprises the metallocene compound (W) , preferably one of the metallocene compounds (W-1) to (W-5).

Specifically, the olefin polymerization catalyst comprises:

(A) the metallocene compound (W) and

(B) at least one compound selected from: (B-1) an organometallic compound, (B-2) an organoaluminum oxy-compound and (B-3) a compound which reacts with the metallocene compound (A) to form an ion pair.

A method for olefin polymerization according to the invention is dedicated for polymerization of one or more monomers selected from ethylene and .alpha.-olefins, in which ethylene is an essential monomer. The polymerization is carried out in the presence of an olefin polymerization catalyst which contains the bridged metallocene compound (W) of the formula [I] so that an ethylene based polymer with an ethylene content of more than 50 mol % is obtained.

In another embodiment, the method for olefin polymerization is dedicated for polymerization of one or more monomers selected from ethylene and .alpha.-olefins, in which ethylene is an essential monomer. The polymerization is carried out in the presence of an olefin polymerization catalyst which contains the bridged metallocene compound (W') of the formula [I'] so that an ethylene based polymer with an ethylene content of more than 50 mol % is obtained.

##STR00007##

In the formula [I'], Y is a carbon, silicon, germanium or tin atom; M is Ti, Zr or Hf; R.sup.1 to R.sup.12, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group; R.sup.5 to R.sup.12 cannot be hydrogen at the same time; neighboring substituents of R.sup.5 to R.sup.12 may be linked with each other to form a ring; R.sup.13 and R.sup.14, which may be the same or different, are each a hydrocarbon group or a silicon-containing group and may be linked with each other to form a ring; Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and maybe the same or different when plural; and j is an integer from 1 to 4.

The bridged metallocene compounds (W') of the formula [I'] in which R.sup.13 and R.sup.14 are phenyl, methyl or pentamethylene groups, are defined as metallocene compounds (T), most of which are already well known.

In the method for olefin polymerization, the metallocene compound (W) or (W') of the formula [I] or [I'] may have been supported on a carrier.

BEST MODE TO CARRY OUT THE INVENTION

The metallocene compounds, production thereof, olefin polymerization catalyst containing the metallocene compound, and method for olefin polymerization using the olefin polymerization catalyst will be described hereinafter.

Metallocene Compound

The metallocene compounds can be categorized into the following two major types:

1st category: novel metallocene compounds (W) useful as a constituent of catalyst for polymerization of essential ethylene and other optional olefins

2nd category: metallocene compounds (T) useful as a constituent of catalyst for polymerization of essential ethylene and other optional olefins.

The "essential ethylene" as used herein means that ethylene is essentially used as a monomer for polymerization optionally with at least one .alpha.-olef in so that an ethylene based polymer with an ethylene content of more than 50 mol % is obtained.

The metallocene compounds (W) of 1st category are novel in the art. Therefore, the olefin polymerization catalyst containing the metallocene compound (W), and the method for polymerization of the olefins in the presence of the olefin polymerization catalyst are also novel in the art.

The metallocene compounds (T) of 2nd category are known in the art. However, there has been no technology for polymerization of the olefins in the presence of the olefin polymerization catalyst which contains the metallocene compound (T).

In the present invention, the metallocene compound as a constituent of the olefin polymerization catalyst may be the metallocene compound (W) of 1st category or the metallocene compound (T) of 2nd category.

Metallocene Compound (W)

The metallocene compound (W) is represented by the formula [I]:

##STR00008## wherein Y is a carbon, silicon, germanium or tin atom; M is Ti, Zr or Hf; R.sup.1 to R.sup.12, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group; and neighboring substituents of R.sup.5 to R.sup.12 may be linked with each other to form a ring.

The hydrocarbon group is preferably of 1 to 20 carbon atoms. Examples thereof include alkyl, alkenyl, alkynyl and aryl groups which consist of carbon and hydrogen; and corresponding groups to the above groups in which part of hydrogen atoms connected with carbon is substituted with a halogen atom or an oxygen-, nitrogen- or silicon-containing group, or in which arbitrary two adjacent hydrogen atoms are both substituted to form an alicyclic or aromatic ring.

Examples of the hydrocarbon group of 1 to 20 carbon atoms include linear hydrocarbon groups, such as methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decanyl groups; branched hydrocarbon groups, such as isopropyl, isobutyl, s-butyl, t-butyl, t-amyl, neopentyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-dipropylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl and cyclopropylmethyl groups; cyclic saturated hydrocarbon groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl and adamantyl groups; cyclic unsaturated hydrocarbon groups, such as phenyl, naphthyl, biphenyl, phenanthryl and anthracenyl groups; saturated hydrocarbon groups which are substituted with aryl groups, such as benzyl and cumyl groups; oxygen-containing hydrocarbon groups, such as methoxy, ethoxy and phenoxy groups; nitrogen-containing hydrocarbon groups, such as N-methylamino, N,N-dimethylamino and N-phenylamino groups; and halogen-containing hydrocarbon groups, such as trifluoromethyl, tribromomethyl, pentafluoroethyl and pentafluorophenyl groups.

Examples of the silicon-containing group include cyclopentadienyl, indenyl and fluorenyl groups in which the ring carbon has a direct covalent bond with silicon. Specific examples include alkylsilyl groups, such as trimethylsilyl and triethylsilyl groups, and arylsilyl groups.

R.sup.13 and R.sup.14, which may be the same or different, are each a hydrocarbon group or a silicon-containing group and may be linked with each other to form a ring. Examples of the hydrocarbon group and silicon-containing group are as listed above.

For example, such metallocene compounds (W--R) can be represented by the formula [I-R]:

##STR00009## wherein A is a divalent hydrocarbon group of 2 to 20 carbon atoms optionally with an unsaturated bond, and may have two or more ring structures containing the A-Y ring depicted above. Examples of the ring structure include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo[3.3.1]nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanylidene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene and cycloheptamethylenesilylene.

An important feature in the metallocene compound (W) of the formula [I] is that R.sup.13 and are hydrocarbon groups other than phenyl, methyl and pentamethylene groups when (i) R.sup.5 to R.sup.12 are all hydrogen or when (ii) R.sup.6 and R.sup.11 are both hydrocarbon groups. The metallocene compound with such condition is more preferable as a constituent for the olefin polymerization catalyst.

Another important feature is that R.sup.13 and R.sup.14 are hydrocarbon groups other than phenyl and methyl groups when R.sup.7 and R.sup.10 are both hydrocarbon groups. The metallocene compound with such condition is more preferable as a constituent for the olefin polymerization catalyst.

Q is a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination by a lone pair of electrons, and may be the same or different when plural. j is an integer from 1 to 4.

Examples of the halogen include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group are as listed above.

Examples of the anionic ligand include alkoxy groups, such as methoxy, tert-butoxy and phenoxy; carboxylate groups, such as acetate and benzoate; and sulfonate groups, such as mesylate and tosylate.

Examples of the neutral ligand capable of coordination by a lone pair of electrons include organophosphorus compounds, such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine; and ethers, such as tetrahydrofuran, diethylether, dioxane and 1,2-dimethoxyethane. When Q is plural, at least one is preferably the halogen or alkyl group.

The preferable metallocene compounds (W-1) to (W-5) will be sequentially described.

Metallocene compound (W-1)

The metallocene compound (W-1) is represented by the formula [I-1]:

##STR00010## wherein R.sup.1 to R.sup.12 which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group; and neighboring substituents of R.sup.1 to R.sup.12 may be linked with each other to form a ring. Examples of the hydrocarbon group and the silicon-containing group are as defined with respect to the metallocene compound (W). In the formula [I-1] , R.sup.1 to R.sup.4 are preferably all hydrogen; M is Ti or Zr; Y is a Group 14 atom, preferably carbon or silicon; R.sup.13 is an unsubstituted or substituted aryl group; and R.sup.14 is a substituted aryl group. The "unsubstituted aryl group" as used herein can be defined as a group in which all the aromatic nucleus carbons except the one linked with Y are linked with hydrogen. The "substituted aryl group" as used herein can be defined as a group in which at least one of the aromatic nucleus carbons except the one linked with Y is linked with an atom or a group other than hydrogen. Examples of the aryl group include phenyl, naphthyl and anthracenyl groups, with a phenyl group preferable.

Examples of the substituent for the substituted aryl group include hydrocarbon groups of 1 to 20 carbon atoms, halogens and silicon-containing groups. Exemplary hydrocarbon groups of 1 to 20 carbon atoms are alkyl, alkenyl, alkynyl and aryl groups which consist of carbon and hydrogen; and corresponding groups to the above groups in which part of hydrogen atoms connected with carbon is substituted with a halogen atom or an oxygen-, nitrogen- or silicon-containing group, or in which arbitrary two adjacent hydrogen atoms are both substituted to form an alicyclic ring.

Specific examples of the hydrocarbon groups of 1 to 20 carbon atoms as substituents include linear hydrocarbon groups, such as methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decanyl groups; branched hydrocarbon groups, such as isopropyl, isobutyl, s-butyl, t-butyl, t-amyl, neopentyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-dipropylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl and cyclopropylmethyl groups; cyclic saturated hydrocarbon groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl and adamantyl groups; cyclic unsaturated hydrocarbon groups, such as phenyl, naphthyl, biphenyl, phenanthryl and anthracenyl groups; saturated hydrocarbon groups which are substituted with aryl groups, such as benzyl and cumyl groups; oxygen-containing hydrocarbon groups, such as methoxy, ethoxy and phenoxy groups; nitrogen-containing hydrocarbon groups, such as N-methylamino, N,N-dimethylamino and N-phenylamino groups; and halogen-containing hydrocarbon groups, such as trifluoromethyl, tribromomethyl, pentafluoroethyl and pentafluorophenyl groups.

Examples of the halogens as substituents include fluorine, chlorine, bromine and iodine. Examples of the silicon-containing groups as substituents include trimethylsilyl and triethylsilyl groups.

The aryl group with these substituents, i.e., the substituted aryl group, is preferably substituted with hydrocarbon groups of 1 to 6 carbon atoms selected from methyl, ethyl, n-propyl, isopropyl, cyclopropylmethyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, t-amyl, neopentyl, n-hexyl, 3-methylpentyl, 1-methyl-1-ethylpropyl, cyclohexyl, phenyl, pentafluorophenyl and trifluoromethyl groups. Of the above substituted aryl groups, tolyl, t-butylphenyl, dimethylphenyl, (trifluoromethyl)phenyl and bis(trifluoromethyl)phenyl groups are more preferable. Particularly, the substituted phenyl group preferably has the above substituents at the meta and/or para position(s).

When R.sup.13 is the substituted aryl group, R.sup.13 and R.sup.14 may be the same or different.

Q and j are as defined in the formula [I] for the metallocene compound (W).

Examples of the compounds having the above characteristics in the chemical structure include di(p-tolyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconi- um dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconi- um dichloride, di(p-tert-butylphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(p-tert-butylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluore- nyl)zirconium dichloride, di(p-tert-butylphenyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)z- irconium dichloride, di(p-tert-butylphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluore- nyl)zirconium dichloride, di(p-n-butylphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(p-n-butylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl- )zirconium dichloride, di(p-n-butylphenyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)zirc- onium dichloride, di(p-n-butylphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl- )zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconi- um dichloride, di(m-tolyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconi- um dichloride, (p-tolyl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(p-isopropylphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(p-tert-butylphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dimethyl, di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodiben- zofluorenyl)zirconium dichloride, (p-tolyl)(phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofl- uorenyl)zirconium dichloride, di(p-isopropylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodiben- zofluorenyl)zirconium dichloride, di(p-tert-butylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibe- nzofluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluoreny- l)zirconium dimethyl, (p-tolyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)z- irconium dichloride, di(p-isopropylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren- yl)zirconium dichloride, di(p-tert-butylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluore- nyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconi- um dimethyl, (p-tolyl)(phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)z- irconium dichloride, di(p-isopropylphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoren- yl)zirconium dichloride, di(p-tert-butylphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluore- nyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconi- um dimethyl, (p-tert-butylphenyl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)zirconi- um dichloride, (p-tert-butylphenyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butyl- fluorenyl)zirconium dichloride, (p-tert-butylphenyl)(phenyl)methylene(cyclopentadienyl)(2,7-dimethylfluor- enyl)zirconium dichloride, (p-tert-butylphenyl)(phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butyl- fluorenyl)zirconium dichloride, (p-ethylphenyl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, (p-ethylphenyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluor- enyl)zirconium dichloride, (p-ethylphenyl)(phenyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)- zirconium dichloride, (p-ethylphenyl)(phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluor- enyl)zirconium dichloride, (4-biphenyl)(phenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, (4-biphenyl)(phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoreny- l)zirconium dichloride, (4-biphenyl)(phenyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)zir- conium dichloride, (4-biphenyl)(phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoreny- l)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirc- onium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirc- onium dichloride, bis(3,4-dimethylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluor- enyl)zirconium dichloride, bis(3,4-dimethylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodib- enzofluorenyl)zirconium dichloride, bis(3,5-dimethylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluor- enyl)zirconium dichloride, bis(3,5-dimethylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodib- enzofluorenyl)zirconium dichloride, bis(4-cyclohexylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluor- enyl)zirconium dichloride, bis(4-cyclohexylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodib- enzofluorenyl)zirconium dichloride, bis{3-(trifluoromethyl)phenyl}methylene(cyclopentadienyl)(2,7-di-tert-but- ylfluorenyl)zirconium dichloride, bis{3-(trifluoromethyl)phenyl}methylene(cyclopentadienyl)(octamethyloctah- ydrodibenzofluorenyl)zirconium dichloride, bis{3,5-bis(trifluoromethyl)phenyl}methylene(cyclopentadienyl)(2,7-di-ter- t-butylfluorenyl)zirconium dichloride, and bis{3,5-bis(trifluoromethyl)phenyl}methylene(cyclopentadienyl)(octamethyl- octahydrodibenzofluorenyl)zirconium dichloride.

Metallocene Compound (W-2)

The metallocene compound (W-2) is represented by the formula [I-2]:

##STR00011## wherein R.sup.1 to R.sup.12, which may be the same or different, are each hydrogen, a hydrocarbon group or a silicon-containing group. The hydrocarbon group and the silicon-containing group are as defined with respect to the metallocene compound (W).

Neighboring substituents of R.sup.1 to R.sup.4 may be linked with each other to form a ring. Examples of the substituted cyclopentadienyl group with the ring(s) include indenyl, 2-methylindenyl, tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,2,4-trimethyltetrahydroindenyl, 4-phenylindenyl, 2-methyl-4-phenylindenyl and fluorenyl. In the formula [I-2], R.sup.1 to R.sup.4 are preferably all hydrogen.

Neighboring substituents of R.sup.5 to R.sup.12 in the fluorene ring may be linked with each other to form a ring. Examples of the substituted fluorenyl group with the ring(s) include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and octamethyltetrahydrodicyclopentafluorenyl groups.

Of the substituents R.sup.5 to R.sup.12 in the fluorene ring, arbitrary two or more groups of R.sup.6, R.sup.7, R.sup.10 and R.sup.11 are preferably hydrocarbon groups of 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, tert-butyl, amyl and n-pentyl groups. In view of easiness in synthesis of ligands, these substituents are preferably symmetrical, i.e., R.sup.6 and R.sup.11, and R.sup.7 and R.sup.10 are the same groups. It is also preferable that R.sup.6and R.sup.7, and R.sup.10 and R.sup.11 form the same aliphatic rings.

In the formula [I-2], Y is a carbon atom; R.sup.13 and R.sup.15 are each the hydrocarbon group or the silicon-containing group; R.sup.14 and R.sup.16 are each hydrogen, the hydrocarbon group or the silicon-containing group; R.sup.13 and R.sup.15, and R.sup.14 and R.sup.16 may be the same or different; R.sup.13 and R.sup.15, and R.sup.14 and R.sup.16 may be linked with each other to form rings; when unlinked, R.sup.13 and R.sup.15, and R.sup.14 and R.sup.16 are preferably the same groups in view of easiness in synthesis of ligands; and R.sup.14 and R.sup.16 are preferably hydrogen, more preferably with R.sup.13 and R.sup.15 being hydrocarbon groups of 3 to 20 carbon atoms. Examples of the hydrocarbon groups of 3 to 20 carbon atoms include n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, m-tolyl, p-tolyl and benzyl groups. Particularly preferably, R.sup.14 and R.sup.16 are both hydrogen and R.sup.13 and R.sup.15 are aryl groups of 6 to 20 carbon atoms. Exemplary aryl groups are phenyl, naphthyl, indenyl, fluorenyl and biphenyl groups, and aromatic nucleus-substituted groups thereof. Phenyl and alkyl-substituted phenyl groups are preferred.

Q and j are as defined in the formula [I] for the metallocene compound (W).

Examples of the metallocene compound (W-2) of the formula [I-2] include di-n-butylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di-n-butylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiu- m dichloride, di-n-butylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiu- m dichloride, di-n-butylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl- )zirconium dichloride, di-n-butylmethylene(cyclopentadienyl)(benzofluorenyl)zirconium dichloride, di-n-butylmethylene(cyclopentadienyl)(dibenzofluorenyl) zirconium dichloride, di-n-butylmethylene(cyclopentadienyl)(octahydrodibenzofluorenyl)zirconium dichloride, di-n-butylmethylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentaflu- orenyl)zirconium dichloride, diisobutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diisobutylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiu- m dichloride, diisobutylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiu- m dichloride, diisobutylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl- )zirconium dichloride, diisobutylmethylene(cyclopentadienyl)(benzofluorenyl)zirconium dichloride, diisobutylmethylene(cyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, diisobutylmethylene(cyclopentadienyl)(octahydrodibenzofluorenyl)zirconium dichloride, diisobutylmethylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentaflu- orenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride (otherwise, 1,3-diphenylisopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, which will be omitted hereinafter), dibenzylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z- irconium dichloride, dibenzylmethylene(cyclopentadienyl)(benzofluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(octahydrodibenzofluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluor- enyl)zirconium dichloride, diphenethylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, diphenethylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconi- um dichloride, diphenethylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconi- um dichloride, diphenethylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluoreny- l)zirconium dichloride, diphenethylmethylene(cyclopentadienyl)(benzofluorenyl)zirconium dichloride, diphenethylmethylene(cyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, diphenethylmethylene(cyclopentadienyl)(octahydrodibenzofluorenyl)zirconiu- m dichloride, diphenethylmethylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafl- uorenyl)zirconium dichloride, di(benzhydryl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(benzhydryl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirc- onium dichloride, di(benzhydryl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirc- onium dichloride, di(benzhydryl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluor- enyl)zirconium dichloride, di(benzhydryl)methylene(cyclopentadienyl)(benzofluorenyl)zirconium dichloride, di(benzhydryl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, di(benzhydryl)methylene(cyclopentadienyl)(octahydrodibenzofluorenyl)zirco- nium dichloride, di(benzhydryl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopent- afluorenyl)zirconium dichloride, di(cumyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(cumyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dichloride, di(cumyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, di(cumyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)- zirconium dichloride, di(cumyl)methylene(cyclopentadienyl)(benzofluorenyl)zirconium dichloride, di(cumyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, di(cumyl)methylene(cyclopentadienyl)(octahydrodibenzofluorenyl)zirconium dichloride, di(cumyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluo- renyl)zirconium dichloride, di(1-phenyl-ethyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(1-phenyl-ethyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)- zirconium dichloride, di(1-phenyl-ethyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)- zirconium dichloride, di(1-phenyl-ethyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof- luorenyl)zirconium dichloride, di(1-phenyl-ethyl)methylene(cyclopentadienyl)(benzofluorenyl)zirconium dichloride, di(1-phenyl-ethyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, di(1-phenyl-ethyl)methylene(cyclopentadienyl)(octahydrodibenzofluorenyl)z- irconium dichloride, di(1-phenyl-ethyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclo- pentafluorenyl)zirconium dichloride, di(cyclohexylmethyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(cyclohexylmethyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoreny- l)zirconium dichloride, di(cyclohexylmethyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoreny- l)zirconium dichloride, di(cyclohexylmethyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenz- ofluorenyl)zirconium dichloride, di(cyclohexylmethyl)methylene(cyclopentadienyl)(benzofluorenyl)zirconium dichloride, di(cyclohexylmethyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconiu- m dichloride, di(cyclohexylmethyl)methylene(cyclopentadienyl)(octahydrodibenzofluorenyl- )zirconium dichloride, di(cyclohexylmethyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyc- lopentafluorenyl)zirconium dichloride, di(1-cyclohexyl-ethyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(1-cyclohexyl-ethyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluore- nyl)zirconium dichloride, di(1-cyclohexyl-ethyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluore- nyl)zirconium dichloride, di(1-cyclohexyl-ethyl)methylene(cyclopentadienyl)(octamethyloctahydrodibe- nzofluorenyl)zirconium dichloride, di(1-cyclohexyl-ethyl)methylene(cyclopentadienyl)(benzofluorenyl)zirconiu- m dichloride, di(1-cyclohexyl-ethyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zircon- ium dichloride, di(1-cyclohexyl-ethyl)methylene(cyclopentadienyl)(octahydrodibenzofluoren- yl)zirconium dichloride, di(1-cyclohexyl-ethyl)methylene(cyclopentadienyl)(octamethyltetrahydrodic- yclopentafluorenyl)zirconium dichloride, di(cyclopentylmethyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(cyclopentylmethyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren- yl)zirconium dichloride, di(cyclopentylmethyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoren- yl)zirconium dichloride, di(cyclopentylmethyl)methylene(cyclopentadienyl)(octamethyloctahydrodiben- zofluorenyl)zirconium dichloride, di(cyclopentylmethyl)methylene(cyclopentadienyl)(benzofluorenyl)zirconium dichloride, di(cyclopentylmethyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconi- um dichloride, di(cyclopentylmethyl)methylene(cyclopentadienyl)(octahydrodibenzofluoreny- l)zirconium dichloride, di(cyclopentylmethyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicy- clopentafluorenyl)zirconium dichloride, di(1-cyclopentyl-ethyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(1-cyclopentyl-ethyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluor- enyl)zirconium dichloride, di(1-cyclopentyl-ethyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluor- enyl)zirconium dichloride, di(1-cyclopentyl-ethyl)methylene(cyclopentadienyl)(octamethyloctahydrodib- enzofluorenyl)zirconium dichloride, di(1-cyclopentyl-ethyl)methylene(cyclopentadienyl)(benzofluorenyl)zirconi- um dichloride, di(1-cyclopentyl-ethyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirco- nium dichloride, di(1-cyclopentyl-ethyl)methylene(cyclopentadienyl)(octahydrodibenzofluore- nyl)zirconium dichloride, di(1-cyclopentyl-ethyl)methylene(cyclopentadienyl)(octamethyltetrahydrodi- cyclopentafluorenyl)zirconium dichloride, di(naphthylmethyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)- zirconium dichloride, di(naphthylmethyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)- zirconium dichloride, di(naphthylmethyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof- luorenyl)zirconium dichloride, di(naphthylmethyl)methylene(cyclopentadienyl)(benzofluorenyl)zirconium dichloride, di(naphthylmethyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, di(naphthylmethyl)methylene(cyclopentadienyl)(octahydrodibenzofluorenyl)z- irconium dichloride, di(naphthylmethyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclo- pentafluorenyl)zirconium dichloride, di(biphenylmethyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)- zirconium dichloride, di(biphenylmethyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)- zirconium dichloride, di(biphenylmethyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof- luorenyl)zirconium dichloride, di(biphenylmethyl)methylene(cyclopentadienyl)(benzofluorenyl)zirconium dichloride, di(biphenylmethyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, di(biphenylmethyl)methylene(cyclopentadienyl)(octahydrodibenzofluorenyl)z- irconium dichloride, di(biphenylmethyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclo- pentafluorenyl)zirconium dichloride, (benzyl)(phenethyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, (benzyl)(phenethyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl- )zirconium dichloride, (benzyl)(phenethyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl- )zirconium dichloride, (benzyl)(phenethyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzo- fluorenyl)zirconium dichloride, (benzyl)(n-butyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, (benzyl)(n-butyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)z- irconium dichloride, (benzyl)(n-butyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)z- irconium dichloride, (benzyl)(n-butyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofl- uorenyl)zirconium dichloride, (benzyl)(cumyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, (benzyl)(cumyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zir- conium dichloride, (benzyl)(cumyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zir- conium dichloride, (benzyl)(cumyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluo- renyl)zirconium dichloride, (benzyl)(cyclohexylmethyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, (benzyl)(cyclohexylmethyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfl- uorenyl)zirconium dichloride, (benzyl)(cyclohexylmethyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfl- uorenyl)zirconium dichloride, (benzyl)(cyclohexylmethyl)methylene(cyclopentadienyl)(octamethyloctahydro- dibenzofluorenyl)zirconium dichloride, dibenzylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride, dibenzylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)titanium dichloride, dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)titanium dichloride, dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)t- itanium dichloride, dibenzylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride, dibenzylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride, dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)hafnium dichloride, dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)h- afnium dichloride, dibenzylmethylene(cyclopentadienyl)(fluorenyl)zirconium dibromide, dibenzylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium

dibromide, dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dibromide, dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z- irconium dibromide, dibenzylmethylene(cyclopentadienyl)(fluorenyl)zirconium dimethyl, dibenzylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dimethyl, dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)- zirconium dimethyl, dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z- irconium dimethyl, dicyclohexylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, dicyclohexylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zircon- ium dichloride, dicyclohexylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zircon- ium dichloride, dicyclohexylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluoren- yl)zirconium dichloride, (cyclohexyl)(methyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, (cyclohexyl)(methyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoreny- l)zirconium dichloride, (cyclohexyl)(methyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoreny- l)zirconium dichloride, (cyclohexyl)(methyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenz- ofluorenyl)zirconium dichloride, (adamantyl)(methyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, (adamantyl)(methyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl- )zirconium dichloride, (adamantyl)(methyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl- )zirconium dichloride, and (adamantyl)(methyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzo- fluorenyl)zirconium dichloride.

Metallocene compound (W-3)

The metallocene compound (W-3) is represented by the formula [I-3]:

##STR00012## wherein R.sup.1 and R.sup.2, which may be the same or different, are each hydrogen, a hydrocarbon group, a silicon-containing group or a halogen-containing group, preferably both hydrocarbon groups. The hydrocarbon group and the silicon-containing group are as defined with respect to the metallocene compound (W). Examples of the halogen-containing group include fluorine, chlorine, bromine and iodine atoms, and a trifluoromethyl group.

The hydrocarbon group is preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, m-tolyl, p-tolyl, benzyl or cumyl group, particularly a methyl, tert-butyl, phenyl or cumyl group, optimally a tert-butyl group.

n is an integer from 1 to 10, preferably 3 or 4.

Q and j are as defined in the formula [I] for the metallocene compound (W).

Examples of the metallocene compound (W-3) of the formula [I-3] include cyclopropylidene(cyclopentadienyl)(3,6-dimethyl-fluorenyl)zirconium dichloride, cyclobutylidene(cyclopentadienyl)(3,6-dimethyl-fluorenyl)zirconium dichloride, cyclopentylidene(cyclopentadienyl)(3,6-dimethyl-fluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(3,6-dimethyl-fluorenyl)zirconium dichloride, cycloheptylidene(cyclopentadienyl)(3,6-dimethyl-fluorenyl)zirconium dichloride, cyclopropylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, cyclobutylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, cyclopentylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, cycloheptylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, cyclopropylidene(cyclopentadienyl)(3,6-dicumyl-fluorenyl)zirconium dichloride, cyclobutylidene(cyclopentadienyl)(3,6-dicumyl-fluorenyl)zirconium dichloride, cyclopentylidene(cyclopentadienyl)(3,6-dicumyl-fluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(3,6-dicumyl-fluorenyl)zirconium dichloride, cycloheptylidene(cyclopentadienyl)(3,6-dicumyl-fluorenyl)zirconium dichloride, cyclopropylidene(cyclopentadienyl)(3,6-di(trimethylsilyl)-fluorenyl)zirco- nium dichloride, cyclobutylidene(cyclopentadienyl)(3,6-di(trimethylsilyl)-fluorenyl)zircon- ium dichloride, cyclopentylidene(cyclopentadienyl)(3,6-di(trimethylsilyl)-fluorenyl)zirco- nium dichloride, cyclohexylidene(cyclopentadienyl)(3,6-di(trimethylsilyl)-fluorenyl)zircon- ium dichloride, cycloheptylidene(cyclopentadienyl)(3,6-di(trimethylsilyl)-fluorenyl)zirco- nium dichloride, cyclopropylidene(cyclopentadienyl)(3,6-diphenyl-fluorenyl)zirconium dichloride, cyclobutylidene(cyclopentadienyl)(3,6-diphenyl-fluorenyl)zirconium dichloride, cyclopentylidene(cyclopentadienyl)(3,6-diphenyl-fluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(3,6-diphenyl-fluorenyl)zirconium dichloride, cycloheptylidene(cyclopentadienyl)(3,6-diphenyl-fluorenyl)zirconium dichloride, cyclopropylidene(cyclopentadienyl)(3,6-dibenzyl-fluorenyl)zirconium dichloride, cyclobutylidene(cyclopentadienyl)(3,6-dibenzyl-fluorenyl)zirconium dichloride, cyclopentylidene(cyclopentadienyl)(3,6-dibenzyl-fluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(3,6-dibenzyl-fluorenyl)zirconium dichloride, cycloheptylidene(cyclopentadienyl)(3,6-dibenzyl-fluorenyl)zirconium dichloride, cyclopropylidene(cyclopentadienyl)(3,6-difluorofluorenyl)zirconium dichloride, cyclobutylidene(cyclopentadienyl)(3,6-difluorofluorenyl)zirconium dichloride, cyclopentylidene(cyclopentadienyl)(3,6-difluorofluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(3,6-difluorofluorenyl)zirconium dichloride, cycloheptylidene(cyclopentadienyl)(3,6-difluorofluorenyl)zirconium dichloride, cyclopropylidene(cyclopentadienyl)(3,6-dibromofluorenyl)zirconium dichloride, cyclobutylidene(cyclopentadienyl)(3,6-dibromofluorenyl)zirconium dichloride, cyclopentylidene(cyclopentadienyl)(3,6-dibromofluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(3,6-dibromofluorenyl)zirconium dichloride, cycloheptylidene(cyclopentadienyl)(3,6-dibromofluorenyl)zirconium dichloride, cyclopropylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dibromide, cyclobutylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dibromide, cyclopentylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dibromide, cyclohexylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dibromide, cycloheptylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dibromide, cyclopropylidene(cyclopentadienyl)(3,6-dimethyl-fluorenyl)zirconium dimethyl, cyclobutylidene(cyclopentadienyl)(3,6-dimethyl-fluorenyl)zircon- ium dimethyl, cyclopentylidene(cyclopentadienyl)(3,6-dimethyl-fluorenyl)zirconium dimethyl, cyclohexylidene(cyclopentadienyl)(3,6-dimethyl-fluorenyl)zircon- ium dimethyl, cycloheptylidene(cyclopentadienyl)(3,6-dimethyl-fluorenyl)zirconium dimethyl, cyclopropylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)h- afnium dichloride, cyclobutylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)hafnium dichloride, cyclopentylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)hafnium dichloride, cyclohexylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)hafnium dichloride, cycloheptylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)titanium dichloride, cyclopropylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)titanium dichloride, cyclobutylidene(cyc