Organic compounds -- part of the class 532-570 series – Organic compounds – Radioactive metal containing
Reexamination Certificate
2000-10-12
2002-11-12
Jones, Dameron L. (Department: 1619)
Organic compounds -- part of the class 532-570 series
Organic compounds
Radioactive metal containing
C534S011000, C534S014000, C534S015000, C556S047000, C556S143000, C562S428000, C502S117000
Reexamination Certificate
active
06479646
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to new metallocene compounds useful as a catalyst component for olefin polymerization. More particularly, the invention relates to metallocene compounds having an indenyl ligand substituted by a heteroaromatic group and catalysts for olefin polymerization containing said metallocene compounds.
BACKGROUND OF THE INVENTION
As a catalyst component which can be used in the polymerization of olefins, conventional Ziegler-Natta catalysts have been partly replaced by the metallocene compounds wherein a multidentate compound containing a &pgr;-electron donor such as unsubstituted or substituted cycloalkadienyl groups is coordinated to a transition metal atom, said cycloalkadienyl groups including, e.g., unsubstituted or substituted cyclopentadienyl, indenyl, tetrahydroindenyl and fluorenyl groups.
In recent years, various metallocene compounds having an improved olefin polymerization activity per mole of a transition metal atom have been proposed. It is known that polymers of &agr;-olefin having high stereoregularity, in particular, propylene polymers having high stereoregularity can be preferably prepared by using a metallocene compound having a C
2
symmetry as a catalyst component, 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 a high olefin polymerization activity has been continued. Various metallocene compounds have been proposed wherein a heteroatom is introduced into the substituent or the cycloalkadiene ring in the substituted cycloalkadienyl group. For instance, Japanese Patent Kokai 7-258282 discloses metallocene compounds wherein two indenyl ligands are linked to each other through a linking group and a saturated group containing a heteroatom such as nitrogen, phosphorus, arsenic, antimony or bismuth is directly linked to a carbon group at the 2-position of the indenyl groups through the heteroatom, and specifically, dimethylsilanediylbis(2-pyrrolidino-1-indenyl)zirconium dichloride.
Japanese Patent Kokai 8-183814 discloses metallocene compounds wherein two indenyl ligands are linked to each other through a linking group and the indenyl ligand is substituted by a 1-pyrrolyl group, a 1-indolyl group or the like at the 4-position, and specifically, dimethylsilylenebis(4-(1-indolyl)-2-methylindene)zirconium dichloride.
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.
Japanese Patent Publication 9-510745 discloses bis(2-phenylindenyl)zirconium dichloride as a non-bridged indenyl complex capable of producing a stereo block polypropylene which is a elastomeric polyolefin.
DISCLOSURE OF THE INVENTION
Elastomeric polyolefins having a rubber elasticity have attracted the attention of those skilled in the art recently. A new catalyst for efficiently producing elastomeric polyolefins has been desired, but the conventional catalysts as mentioned above do not meet the demands.
An object of the present invention is to provide a catalyst for efficiently producing elastomeric polyolefins having a high heat resistance.
The present inventors have made earnest studies to accomplish the above object and found that elastomeric polyolefins can be produced efficiently by using as a catalyst component metallocene compounds having two indenyl ligands wherein the indenyl ligand is substituted by a heteroaromatic group preferably at a specific position, and also that elastomeric polyolefins with a high heat resistance can be produced efficiently by using as a catalyst component metallocene compounds wherein the indenyl ligand is substituted by a furyl group at the 2-position.
The present invention relates to a metallocene compound having an indenyl ligand represented by the following formula (1)
wherein M represents a transition metal atom in Group 3 including lanthanoid and actinoid series, or Group 4 or 5 of the periodic table;
each Ra independently represents 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;
each R
1
independently represents a halogen atom, a hydrocarbon group of 1-20 carbons, a halogenated hydrocarbon group of 1-20 carbons, 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, and adjacent R
1
's may be joined together to form a ring of 6-8 carbons;
p and q are each independently an integer of 1-7;
n and l are each independently 0 or an integer of 1-6; and
X each independently represents a halogen atom, a hydrocarbon group of 1-20 carbons, a halogenated hydrocarbon group of 1-20 carbons, or a silyl group substituted by said hydrocarbon group or said halogenated hydrocarbon group; and a catalyst for olefin polymerization comprising said metallocene compound.
DETAILED DESCRIPTION OF THE INVENTION
In the formula (1) which represents the metallocene compounds of the present invention, M represents a transition metal atom in Group 3 including lanthanoid and actinoid series, or Group 4 or 5 of the periodic table, and preferably, titanium, zirconium or hafnium.
Each Ra independently represents 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, which links to the 5- or 6-membered ring of the indenyl ligand. For example, the monocyclic or polycyclic heteroaromatic groups containing an oxygen atom can include furyl and benzofuryl, and furyl groups can include 2-furyl and 3-furyl.
The monocyclic or polycyclic heteroaromatic groups containing a sulfur atom can include thienyl and benzothienyl, and thienyl groups can include 2-thienyl and 3-thienyl.
The monocyclic or polycyclic heteroaromatic groups containing a nitrogen atom can include pyrrolyl, pyridyl, indolyl and quinolyl. Pyrrolyl groups can include 1-pyrrolyl, 2-pyrrolyl and 3-pyrrolyl; pyridyl groups can include 2-pyridyl, 3-pyridyl and 4-pyridyl; indolyl groups can include 1-indolyl and 3-indolyl; and quinolyl groups can include 1-quinolyl and 3-quinolyl.
The heteroaromatic group Ra may be substituted by a substituent such as an alkyl group, an aryl group, an aralkyl group, an alkoxy group, a substituted silyl group and a halogen atom. The adjacent substituents may be joined together to form a condensed ring. Typical examples of the substituents can include methyl, ethyl, tert-butyl, phenyl, vinyl, methoxy, trimethylsilyl, vinyldimethylsilyl, phenyldimethylsilyl, methoxydimethylsilyl and fluoro. A typical example of the condensed ring is a benzene ring.
Preferable heteroaromatic groups are 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, benzofuryl, benzothienyl, 3-indolyl, 1-quinolyl and 3-quinolyl. More preferable is furyl and particularly preferable is 2-furyl.
Unsubstituted or substituted 2-furyl groups can include 2-furyl, 2-(5-methyl)furyl, 2-(5-t-butyl)furyl, 2-(5-trimethylsilyl)furyl, 2-(5-phenyl)furyl, 2-(5-vinyldimethylsilyl)furyl, 2-(4,5-benzofuryl), 2-(4,5-dimethyl)furyl and 2-(5-fluoro)furyl. For the production of elastomeric polyolefins with a high heat resistance, it is preferable that at least one of these heteroaromatic groups is linked to the 5-membered ring of the indenyl ligand. More preferably, the heteroaromatic group is linked at the 2-position of the indenyl ligand.
Preferable metallocene compounds of the present invention are the compounds of the formula (1) wherein two heteroaromatic group Ra's are furyl and each furyl group is bonded at the 2-position of two indenyl ligands.
More preferable metallocene compounds of th
Mitani Seiki
Nakano Masato
Ushioda Tsutomu
Yamazaki Hiroshi
Chisso Corporation
Jones Dameron L.
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
LandOfFree
Metallocene compounds having indenyl ligand and catalysts... 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 having indenyl ligand and catalysts..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Metallocene compounds having indenyl ligand and catalysts... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2955010