Hafnium transition metal catalyst compounds, catalyst...

Details Hafnium transition metal catalyst compounds, catalyst... Hafnium transition metal catalyst compounds, catalyst...

1999-10-22

2001-10-09

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S127000, C526S159000, C526S129000, C526S172000, C526S348200, C526S348500, C526S348600, C526S351000, C526S352000

Reexamination Certificate

active

06300438

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a Group 15 containing hafnium transition metal catalyst compound, a catalysts system thereof and its 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 bulky ligand metallocene-type catalyst systems.
More 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 aminodiainide 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.
Furthermore, 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. In addition, 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.
While all these compounds have been described in the art, there is still a need for an improved catalyst compound.
SUMMARY OF THE INVENTION
This invention provides for an improved catalyst compound, a catalyst system and for its use in a polymerizing process.
In one embodiment, the invention is directed to a Group 15 containing hafnium catalyst compound, a catalyst system including the Group 15 containing catalyst compound and to their use in the polymerization of olefin(s).
In another embodiment, the invention is directed to a Group 15 containing bidentate or tridentate ligated hafnium transition metal catalyst compound, a catalyst system including the bidentate or tridentate ligated hafnium metal catalyst compound and to their use in the polymerization of olefin(s).
In another embodiment, the invention is directed to a catalyst compound having a hafnium transition metal 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, a catalyst system of this hafnium transition metal compound and to their use in the polymerization of olefin(s).
In still another embodiment, the invention is directed to a method for supporting the multidentate hafnium based catalysts system, and to the supported catalyst system itself.
In another embodiment, the invention is directed to a process for polymerizing olefin(s), particularly in a gas phase or slurry phase process, utilizing any one of the catalyst systems or supports catalyst systems discussed above.
DETAILED DESCRIPTION OF THE INVENTION
Introduction
It has unexpectedly been found that the hafnium based Group 15 containing catalyst compounds exhibit much higher catalyst productivity as compared to their zirconium or titanium 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 hafnium catalyst compounds of the invention provide for an 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. This in fact is the case with the zirconium analogs of the Group 15 containing hafnium compounds of the invention. As a result of this detrimental effect, the zirconium analogs are not well suited to being supported. However, as a result of the substantially higher activity of the hafnium based multidentate catalyst compounds of this invention, these catalysts compounds are supportable and retain commercially useful productivities.
Group 15 Containing Hafnium Catalyst Compound and Catalyst Systems
In one embodiment, the hafnium based catalyst compounds of the invention are Group 15 bidentate or tridentate ligated hafnium transition metal compound, the preferred Group 15 elements are nitrogen and/or phosphorous, most preferably nitrogen.
The Group 15 containing hafnium catalyst compounds of the invention generally include a hafnium 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.
In one preferred embodiment, at least one of the Group 15 atoms is also bound to a Group 15 or 16 atom through another group, which may be a hydrocarbon group, preferably a hydrocarbon group having 1 to 20 carbon atoms, a heteroatom containing group, preferably silicon, germanium, tin, lead, or phosphorus. In this embodiment, it is further preferred that the Group 15 or 16 atom be bound to nothing or a hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group. Additionally in these embodiment, it is preferred that each of the two Group 15 atoms are also bound to a cyclic group that may optionally be bound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a heteroatom containing group.
In an embodiment of the invention, the Group 15 containing hafnium compound of the invention is represented by the formulae:
wherein
M is hafnium; each X is independently a leaving group, preferably, an anionic leaving group, and more preferably hydrogen, a hydrocarbyl group, a heteroatom or a halogen, and most preferably an alkyl;
y is 0 or 1 (when y is 0 group L′ is absent);
n is the oxidation state of M, preferably +2, +3 or +4, and more preferably +4;
m is

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