Group 15 containing transition metal catalyst compounds,...

Details Group 15 containing transition metal catalyst compounds,... Group 15 containing transition metal catalyst compounds,...

1999-11-08

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, C526S941000, C526S943000, C526S901000, C526S351000, C526S352000, C526S172000

Reexamination Certificate

active

06300439

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a Group 15 containing transition metal catalyst compounds, 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, June 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.
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 transition metal catalyst compound having a substituted hydrocarbon leaving group, 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 transition metal catalyst compound, a catalyst system including the bidentate or tridentate ligated 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 metal 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 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 metal 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 metal based Group 15 containing catalyst compound having a substituted hydrocarbon leaving group exhibit much higher catalyst productivity as compared to the same compounds having halogen or simple alkyl leaving groups. 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 of the invention provide for an improved supported catalysts system, particularly for use in slurry phase or gas phase polymerizations.
Group 15 Containing Metal Catalyst Compound and Catalvst Systems
In one embodiment, the metal based catalyst compounds of the invention are Group 15 bidentate or tridentate ligated transition metal compound having at least one substituted hydrocarbon group, the preferred Group 15 elements are nitrogen and/or phosphorus, most preferably nitrogen, and the preferred leaving group is a substituted alkyl group having greater than 6 carbon atoms, preferably the alkyl substituted with an aryl group.
The Group 15 containing metal catalyst compounds of the invention generally include a transition metal atom bound to at least one substituted hydrocarbon 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 metal compound of the invention is represented by the formulae:
wherein M is a metal, preferably a transition metal, more preferably a Group 4,5 or 6 metal, even more preferably a Group 4 metal, and most preferably hafnium or zirconium; 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; and at least one X is a substituted hydrocarbon group, preferably a substituted alkyl group having more than 6 carbon atoms, most preferably an aryl substituted alkyl group. The most preferred aryl substituted alkyl group is benzyl.
y is 0 or 1 (when y is 0 group L′

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