Metallocene compounds, processes for the preparation...

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

1999-11-30

2001-12-04

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C548S103000, C548S403000, C549S003000, C549S206000, C526S126000, C526S160000, C526S351000, C526S943000, C556S011000, C556S012000, C556S053000, C502S103000, C502S117000, C502S120000

Reexamination Certificate

active

06326493

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 wherein a multidentate compound containing a cycloalkadienyl ring substituted by a heteroaromatic group is coordinated to a Group VIB transition metal atom of the Periodic Table, 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 i-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 cycloalkadienyl group selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a benzoindenyl group, a fluorenyl group and an azulenyl group;
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;
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, the heteroaromatic group being optionally substituted by R
1
as defined above;
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
7
)(R
1
)
m
(Ra)
p
, (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.
The present invention also provides a process for the preparation of said metallocene compound.
Further, the invention provides a catalyst for olefin polymerization comprising said metallocene compound and an aluminoxane. The invention further provides 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: 6169051 (2001-01-01), Mitani et al.
patent: 7-258282 (1995-10-01), None
patent: 8-183814 (1996-07-01), None
“Elastomeric Polypropylene from Unbridge 2-Arylindenyl Zirconocenes: Modeling Polymerization Behavior Using ansa-Metallocene Analogues” by Petoff et al., J. Am. Chem. Soc, 1998, vol. 120, pp. 11316-11322.
“Polymerization Catalysts with Cyclopentadienyl Ligands Ring-Fused to Pyrrole and Thiophene Heterocycles” by Ewen et al., J. Am. Chem. Soc., 1998, vol. 120, pp. 10786-10787.

Affiliated with

Also associated with

Rating

Metallocene compounds, processes for the preparation... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Metallocene compounds, processes for the preparation..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Metallocene compounds, processes for the preparation... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2572139