Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2001-08-31
2003-06-17
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S155000, C502S117000, C526S131000, C526S134000, C526S135000, C526S172000
Reexamination Certificate
active
06579823
ABSTRACT:
FIELD OF THE INVENTION
The present invention generally relates to catalyst compositions useful for the polymerization or oligomerization of olefins, and to processes using the catalyst compositions. Certain of these catalyst compositions comprise a Group 8-10 metal complex comprising a bidentate or variable denticity ligand comprising one or two nitrogen donor atom or atoms independently substituted by an aromatic or heteroaromatic ring(s), wherein the ortho positions of said ring(s) are substituted by aryl or heteroaryl groups.
BACKGROUND OF THE INVENTION
Olefin polymers are used in a wide variety of products, from sheathing for wire and cable to film. Olefin polymers are used, for instance, in injection or compression molding applications, in extruded films or sheeting, as extrusion coatings on paper, for example photographic paper and digital recording paper, and the like. Improvements in catalysts have made it possible to better control polymerization processes and, thus, influence the properties of the bulk material. Increasingly, efforts are being made to tune the physical properties of plastics for lightness, strength, resistance to corrosion, permeability, optical properties, and the like, for particular uses. Chain length, polymer branching and functionality have a significant impact on the physical properties of the polymer. Accordingly, novel catalysts are constantly being sought in attempts to obtain a catalytic process for polymerizing olefins which permits more efficient and better-controlled polymerization of olefins.
The use of late transition metal complexes as catalysts for olefin polymerization has recently been reviewed by Ittel et al. (
Chem. Rev.
2000, 100, 1169). Notwithstanding the many advances described therein, there remains a need for new late transition metal catalysts and processes with improved productivities under the elevated temperatures and pressures of commercial reactor operating conditions. New catalysts and processes for these purposes are described herein.
SUMMARY OF THE INVENTION
In a first aspect, this invention relates to a catalyst composition useful for the polymerization of olefins, which comprises a Group 8-10 metal complex comprising a bidentate or variable denticity ligand comprising two nitrogen donor atoms independently substituted by aromatic or heteroaromatic rings, wherein the ortho positions of the rings are substituted by aryl or heteroaryl groups.
In a second aspect, this invention relates to a catalyst composition comprising either (i) a compound of formula ee1, (ii) the reaction product of a metal comples of formula ff1 and a second compound Y
1
, or (iii) the reaction product of Ni(1,5-cycloocatadiene)
2
, B(C
6
F
5
)
3
, a ligand selected from Set 18, and optionally an olefin;
wherein:
L
2
is selected from Set 18;
T is H, hydrocarbyl, substituted hydrocarbyl, or other group capable of inserting an olefin;
L is an olefin or a neutral donor group capable of being displaced by an olefin; in addition, T and L may be taken together to form a &pgr;-allyl or &pgr;-benzyl group;
X
−
is BF
4
−
, B(C
6
F
5
)
4
−
, BPh
4
−
, or another weakly coordinating anion;
Q and W
1
are each independently fluoro, chloro, bromo or iodo, hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl, heteroatom attached substituted hydrocarbyl, or collectively sulfate, or may be taken together to form a &pgr;-allyl, &pgr;-benzyl, or acac group, in which case a weakly coordinating counteranion X
−
is also present;
Y
1
is either (i) a metal hydrocarbyl capable of abstracting acac from ff1 in exchange for alkyl or another group capable of inserting an olefin, (ii) a neutral Lewis acid capable of abstracting Q or W
1
from ff1 to form a weakly coordinating anion, a cationic Lewis acid whose counterion is a weakly coordinating anion, or a Bronsted acid whose conjugate base is a weakly coordinating anion, or (iii) a Lewis acid capable of reacting with a &pgr;-allyl or it-benzyl group, or a substituent thereon, in ff1 to initiate olefin polymerization;
R
3a,b
are each independently H, alkyl, hydrocarbyl, substituted hydrocarbyl, 2,4,6-triphenylphenyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or fluoroalkyl; and
Ar
1a-d
are each independently phenyl, 4-alkylphenyl, 4-tert-butylphenyl, 4-trifluoromethylphenyl, 4-hydroxyphenyl, 4-(heteroatom attached hydrocarbyl)-phenyl, 4-(heteroatom attached substituted hydrocarbyl)-phenyl, or 1-naphthyl.
In a first preferred embodiment of this second aspect, the metal complex of formula ff1 is selected from Set 19;
wherein:
R
3a,b
are each independently H, methyl, phenyl, 4-methoxyphenyl, or 4-tert-butylphenyl;
Ar
1a-d
are each independently phenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-trifluoromethylphenyl, 1-naphthyl, 2-naphthyl, or 4-phenylphenyl; and
X
−
is BF
4
−
, B(C
6
F
5
)
4
−
, BPh
4
−
, or another weakly coordinating anion.
In a second preferred embodiment of this second aspect, the substituents Ar
1a-d
are 4-tert-butylphenyl or 1-naphthyl. In a third, especially preferred, embodiment, the catalyst composition further comprises a solid support.
In a third aspect, this invention relates to a process for the polymerization of olefins, comprising contacting one or more olefins with the catalyst composition of the second aspect. In a preferred embodiment, of this second aspect, the second compound Y
1
is trimethylaluminum, and the metal complex is contacted with the trimethylaluminum in a gas phase olefin polymerization reactor.
In a fourth aspect, this invention relates to a compound of formula ii1;
wherein:
R
3a,b
are each independently H, methyl, phenyl, 4-methoxyphenyl, or 4-tert-butylphenyl; and
Ar
1a-d
are each independently phenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-trifluoromethylphenyl, 1-naphthyl, 2-naphthyl, or 4-phenylphenyl. Compounds of this formula are useful as ligands in constituting the catalysts of the present invention.
In a fifth aspect, the invention relates to a process for the polymerization of olefins, comprising contacting one or more olefins with a catalyst composition comprising a Group 8-10 transition metal complex which comprises a ligand selected from Set 20;
wherein:
R
2x,y
are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl; in addition, R
2x
and R
2y
may be linked by a bridging group;
R
3a-f
are each independently H, alkyl, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or fluoroalkyl; and
Ar
1a-d
are each independently phenyl, 4-alkylphenyl, 4-tert-butylphenyl, 4-trifluoromethylphenyl, 4-hydroxyphenyl, 4-(heteroatom attached hydrocarbyl)-phenyl, 4-(heteroatom attached substituted hydrocarbyl)-phenyl, 1-naphthyl, 2-naphthyl, 9-anthracenyl, or aryl.
In a sixth aspect, this invention relates to a compound selected from Set 21;
wherein:
R
2x,y
are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl; in addition, R
2x
and R
2y
may be linked by a bridging group;
R
3a-f
are each independently H, alkyl, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, or fluoroalkyl; and
Ar
1a-d
are each independently phenyl, 4-alkylphenyl, 4-tert-butylphenyl, 4-trifluoromethylphenyl, 4-hydroxyphenyl, 4-(heteroatom attached hydrocarbyl)-phenyl, 4-(heteroatom attached substituted hydrocarbyl)-phenyl, 1-naphthyl, 2-naphthyl, 9-anthracenyl, or aryl. These compounds are are useful as ligands in constituting the catalysts of the present invention.
In a seventh aspect, this invention relates to a catalyst composition useful for the polymerization of olefins, which comprises a Group 8-10 transition metal complex comprising a N,N-donor ligand of the formula kk1 or kk2;
wherein:
Ar
2a,b
are each independently aromatic or heteroaromatic groups wherein the
Barrett Anthony Gerard Martin
Killian Christopher Moore
Lavoie Gino Georges
Mackenzie Peter Borden
Moody Leslie Shane
Bell Mark L.
Eastman Chemical Company
Graves, Jr. Esq. Bernard J.
Pasterczyk J.
Wood, Esq. Jonathan D.
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