Transition metal catalyst compounds having deuterium...

Details Transition metal catalyst compounds having deuterium... Transition metal catalyst compounds having deuterium...

2001-12-20

2003-09-23

Wu, David W. (Department: 1713)

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

Catalyst or precursor therefor

Organic compound containing

C502S167000, C502S162000, C526S127000, C526S128000, C526S129000, C526S141000, C526S142000

Reexamination Certificate

active

06624107

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a Group 15 containing transition metal catalyst compounds having a deuterium substituted ligand, catalysts systems thereof and their use in the polymerization of olefin(s).
BACKGROUND OF THE INVENTION
Advances in polymerization and catalysis have resulted in the capability to produce many new polymers having improved physical and chemical properties useful in a wide variety of superior products and applications. With the development of new catalysts the choice of polymerization-type (solution, slurry, high pressure or gas phase) for producing a particular polymer has been greatly expanded. Also, advances in polymerization technology have provided more efficient, highly productive and economically enhanced processes. Especially illustrative of these advances is the development of technology utilizing metallocene catalyst systems.
Recently, developments have lead to the discovery of anionic, multidentate heteroatom ligands as discussed by the following articles: (1) Kempe et al., “Aminopyridinato Ligands—New Directions and Limitations”, 80
th
Canadian Society for Chemistry Meeting, Windsor, Ontario, Canada, Jun. 1-4, 1997; (2) Kempe et al.,
Inorg. Chem.
1996 vol 35 6742; (3) Jordan et al. of polyolefin catalysts based on hydroxyquinolines (Bei, X.; Swenson, D. C.; Jordan, R. F.,
Organometallics
1997, 16, 3282); (4) Horton, et. al., “Cationic Alkylzirconium Complexes Based on a Tridentate Diamide Ligand: New Alkene Polymerization Catalysts”, Organometallics, 1996, 15, 2672-2674 relates to tridentate zirconium complexes; (5) Baumann, et al., “Synthesis of Titanium and Zirconium Complexes that Contain the Tridentate Diamido Ligand [((t-Bu-d
6
)N—O—C
6
H
4
)
2
O]
2−
{[NON}
2−
) and the Living Polymerization of 1-Hexene by Activated [NON]ZrMe2”, Journal of the American Chemical Society, Vol. 119, pp. 3830-3831; (6) Cloke et al., “Zirconium Complexes incorporating the New Tridentate Diamide Ligand [(Me
3
Si)N{CH
2
CH
2
N(SiMe
3
)}
2
]
2−
(L); the Crystal Structure of [Zr(BH
4
)
2
L] and [ZrCl{CH(SiMe
3
)
2
}L]”, J. Chem. Soc. Dalton Trans, pp. 25-30, 1995; (7) Clark et al., “Titanium (IV) complexes incorporating the aminodiamide ligand [(SiMe
3
)N{CH
2
CH
2
N(SiMe
3
)}
2
]
2−
(L); the X-ray crystal structure of [TiMe
2
(L)] and [TiCl{CH(SiMe
3
)
2
}(L)]”, Journal of Organometallic Chemistry, Vol 50, pp. 333-340, 1995; (8) Scollard et al., “Living Polymerization of alpha-olefins by Chelating Diamide Complexes of Titanium”, J. Am. Chem. Soc., Vol 118, No. 41, pp. 10008-10009, 1996; and (9) Guerin et al., “Conformationally Rigid Diamide Complexes: Synthesis and Structure of Titanium (IV) Alkyl Derivatives”, Organometallics, Vol 15, No. 24, pp. 5085-5089, 1996.
U.S. Pat. No. 5,576,460 describes a preparation of arylamine ligands and U.S. Pat. No. 5,889,128 discloses a process for the living polymerization of olefins using initiators having a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. EP 893 454 A1 also describes preferably titanium transition metal amide compounds. U.S. Pat. No. 5,318,935 discusses amido transition metal compounds and catalyst systems especially for the producing isotactic polypropylene. Polymerization catalysts containing bidentate and tridentate ligands are further discussed in U.S. Pat. No. 5,506,184.
In addition, U.S. Pat. No. 6,271,325 discloses a catalyst system comprising a support, an activator and a metal catalyst compound comprising a group 3 to 14 metal atom bound to at least one anionic leaving group and also bound to at least two group 15 atoms, at least one of which is also bound to a group 15 or 16 atom through another group which may be a C
1
to C
20
hydrocarbon group, a heteroatom containing group, silicon, germanium, tin, lead, or phosphorus, wherein the group 15 or 16 atom may also be bound to nothing or a hydrogen, a group 14 atom containing group, a halogen, or a heteroatom containing group, and wherein each of the two group 15 atoms are also bound to a cyclic group and may optionally be bound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a heteroatom containing group.
While all these compounds have been described in the art, there is still a need for an improved polymerization catalyst compounds and for catalyst compositions, having enhanced activity, which include these compounds.
SUMMARY OF THE INVENTION
This invention provides for an improved catalyst compound having a deuterium substituted ligand, a catalyst system including the catalyst compound, and for its use in olefin polymerizing processes.
In one embodiment, the invention is directed to a Group 15 containing metal catalyst compound having a deuterium substituted ligand.
In another embodiment, the invention is directed to a catalyst compound having a transition metal bound to at least one leaving group and also bound to at least two Group 15 atoms, which is also bound to a Group 15 or 16 atom through another group, where at least one of the group 15 atoms is bound to a deuterium atom or to a deuterium atom containing substituent.
In another embodiment, the invention is directed to catalyst systems including processes for polymerizing olefin(s), particularly in a gas phase or slurry phase process, utilizing any one of the catalyst systems or supported catalyst systems discussed above.
DETAILED DESCRIPTION OF THE INVENTION
Introduction
Catalyst deactivation often can involve the cleavage of an X—H bond, where X can be carbon, nitrogen, oxygen, silicon, phosphorus and the like. If this occurs the rate of the reaction may be substantially decreased by substituting the hydrogen atom with a deuterium atom. In addition, substitution of hydrogen by deuterium can affect agostic interactions, which are know to substantially affect polymerization selectivity and kinetics. In the present application, it has been unexpectedly found that Group 15 containing metal catalyst compounds, having a deuterium substituted ligand, exhibit much higher catalyst productivity as compared to their hydrogen-substituted analogs. As a result of this discovery it is now possible to provide a highly active polymerization with commercially acceptable level of productivity.
Furthermore, it has also been discovered that these Group 15 containing metal catalyst compounds, having a deuterium substituted ligand provide for improved supported catalysts system, particularly for use in slurry phase or gas phase polymerizations. It is well known in the art that supporting catalyst compounds typically results in a lowering of the overall catalyst productivity. However, as a result of the substantially higher activity of the deuterium substituted multidentate compounds of the present invention, these catalysts compounds are supportable and retain commercially useful productivities.
For the purposes of this patent specification, the term “catalyst”refers to a metal compound, that when combined with an activator, polymerizes olefins, and the term “catalyst system”refers to the combination of a catalyst, an activator, and optionally a support material.
Group 15 Containing Catalyst Compound and Catalyst Systems
In one embodiment, the deuterium atom containing catalyst compounds of the invention are Group 15 bidentate or tridentate ligated transition metal compound, where at least one Group 15 atom is bound to a deuterium atom or to a deuterium atom containing substituent. The preferred Group 15 elements are nitrogen and/or phosphorous, and more preferably nitrogen.
The Group 15 containing catalyst compounds of the invention generally include a metal atom bound to at least one leaving group and also bound to at least two Group 15 atoms, at least one of which is also bound to a Group 15 or 16 atom through another group, and where at least one of the Group 15 atoms is bound to a deuterium atom or to a deuterium atom containing substituent.
In one embodime

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