Metallocene compounds, processes for the preparation...

Details Metallocene compounds, processes for the preparation... Metallocene compounds, processes for the preparation...

1999-01-25

2001-01-02

Nazario-Gonzalez, Porfirio (Department: 1621)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Plural component system comprising a - group i to iv metal...

C556S011000, C556S012000, C556S053000, C546S004000, C548S103000, C548S403000, C549S003000, C549S206000, C502S117000, C502S120000, C526S126000, C526S160000, C526S351000, C526S943000, C987S002000

Utility Patent

active

06169051

ABSTRACT:

TECHNICAL FIELD
This invention relates to new metallocene compounds useful as a catalyst component for olefin polymerization. More particularly, the invention relates to metallocene compounds consisting of complex compounds wherein a cycloalkadienyl ring-containing multidentate compound substituted on the ring by a heteroaromatic group containing an oxygen, a sulfur or a nitrogen atom is coordinated to a Group VIB transition metal atom and also to the processes for the preparation thereof.
Further, the invention relates to catalysts for olefin polymerization containing said metallocene compounds and processes for the production of olefin polymers using them.
BACKGROUND ART
As a catalyst substituted for Ziegler-Natta catalysts which have been used in the polymerization of olefins, a part of the metallocene compounds is being used which consist of a complex compound wherein a multidentate compound containing a &pgr;-electron donor such as unsubstituted or substituted cycloalkadienyl groups is coordinated to a transition metal atom, the unsubstituted or substituted cycloalkadienyl groups including e.g., unsubstituted or substituted cyclopentadienyl groups, unsubstituted or substituted indenyl groups, unsubstituted or substituted tetrahydroindenyl groups, and unsubstituted or substituted fluorenyl groups.
In recent years, various metallocene compounds have been proposed having higher olefin polymerization activity per mole of a transition metal atom. It is known that the polymers of &agr;-olefin having 3 or more carbon atoms, in particular, propylene polymers, prepared by using a chiral metallocene compound have high stereoregularity, the chiral metallocene compound being the compound wherein a multidentate compound having two substituted cycloalkadienyl groups bonded with a divalent linking group is coordinated to a transition metal atom (J. Am. Chem. Soc. 1998, 120, 11316-11322).
Further, the development of metallocene compounds with high olefin polymerization activity has continued. Various metallocene compounds have been proposed wherein a heteroatom is introduced into the substituent or cycloalkadiene ring in the substituted cycloalkadienyl group.
For instance, Japanese Patent Kokai 7-258282 discloses metallocene compounds wherein the 2-position of the indenyl group is substituted by a saturated group containing a heteroatom such as nitrogen, phosphorus, arsenic, antimony, bismuth or the like, specifically those wherein 2-pyrrolidino-1-indene is linked through a divalent linking group and coordinated to a transition metal atom.
Japanese Patent Kokai 8-183814 discloses chiral metallocene compounds wherein the 4-position of the indenyl group is substituted by unsubstituted or substituted 1-pyrrolyl group, 1-indolyl group or the like, specifically those wherein 4-(1-indolyl)-2-methylindene is linked through a divalent linking group and coordinated to a transition metal atom.
J. Am. Chem. Soc. 1998, 120, 10786-10787 discloses metallocene compounds wherein a heteroatom-containing cycloalkadiene having a thiophene ring or a pyrrol ring condensed to a cyclopentadiene ring is linked through a divalent linking group and coordinated to a transition metal atom.
DISCLOSURE OF THE INVENTION
As mentioned above, there are various proposals for introducing a heteroatom into a &pgr;-electron donor. Except for the compounds disclosed in Japanese Patent Kokai 8-183814, however, the metallocene compounds are not known wherein the substituted cycloalkadienyl group-containing compounds having a heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom on a cycloalkadiene ring, particularly on the 5-membered ring thereof are coordinated to a transition metal atom.
The present invention provides a metallocene compound represented by the following formula (1)
wherein CA
1
represents a substituted cycloalkadienyl group selected from the group consisting of a substituted cyclopentadienyl group, a substituted indenyl group, a substituted tetrahydroindenyl group, a substituted benzoindenyl group and a substituted fluorenyl group; each Ra represents independently a monocyclic or polycyclic heteroaromatic group containing a heteroatom selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom in a 5- or 6-membered ring; each R
1
represents independently a halogen atom, a hydrocarbon group of 1-20 carbons, a halogenated hydrocarbon group wherein a part or all of the hydrogen atoms in the hydrocarbon group are substituted by a halogen atom, a silyl group substituted by said hydrocarbon group or said halogenated hydrocarbon group, an amino group substituted by said hydrocarbon group or a monocyclic or polycyclic amino group;
p is an integer of 1-8;
m is 0 or an integer of 1-8;
Z represents a linking group selected from the group consisting of (CA
2
) (Ra)
q
(R
1
)
n
, —O—, —S—, —NR
1
— and —PR
1
— wherein CA
2
represents an unsubstituted or substituted cycloalkadienyl group; Ra and R
1
have the same meanings as defined above, Ra may be identical with or different from said Ra on CA
1
and R
1
may be identical with or different from said R
1
on CA
1
; and q and n are each independently 0 or an integer of 1-8;
Y represents a divalent linking group selected from the group consisting of —C(R
2
)
2
—, —C
2
(R
2
)
4
—, —C
6
(R
2
)
10
—, —C
6
(R
2
)
4
—, —Si(R
2
)
2
—, —Ge(R
2
)
2
— and —Sn(R
2
)
2
— wherein each R
2
represents independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1-20 carbons, a halogenated hydrocarbon group wherein a part or all of the hydrogen atoms in the hydrocarbon group are substituted by a halogen atom or a silyl group substituted by said hydrocarbon group or said halogenated hydrocarbon group;
M represents a transition metal atom selected from the group consisting of Ti, Zr and Hf; and each X
1
represents independently a halogen atom, a hydrocarbon group of 1-20 carbons, a halogenated hydrocarbon group wherein a part or all of the hydrogen atoms in the hydrocarbon group are substituted by a halogen atom or a silyl group substituted by said hydrocarbon group or said halogenated hydrocarbon group, and a process for the preparation thereof.
Further, the invention provides a catalyst for olefin polymerization comprising said metallocene compound and an aluminoxane, and a process for the production of an olefin polymer wherein an olefin is polymerized in the presence of said olefin polymerization catalyst and in the presence or absence of an organic aluminum compound.


REFERENCES:
patent: 5585509 (1996-12-01), Langhauser et al.
patent: 5840947 (1998-11-01), Kuber et al.
patent: 7-258282 (1995-10-01), None
patent: 8-183814 (1996-07-01), None
“Elastomeric Polypropylene from Unbridged 2-Arylindenyl Zirconocenes: Modeling Polymerization Behavior Using ansa-Metallocene Analogues”, J. Am. Chem. Soc. 1998, vol. 120, pp. 11316-11322.
“Polymerization Catalysts with Cyclopentadienyl Ligands Ring-Fused to Pyrrole and Thiophene Heterocycles”, J. Am. Chem. Soc. 1998, vol. 120, pp. 10786-10787.

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