Catalyst system and its use in a polymerization process

Details Catalyst system and its use in a polymerization process Catalyst system and its use in a polymerization process

1999-11-18

2001-07-24

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, C526S128000, C526S129000, C526S172000, C526S348200, C526S348500, C526S348600

Reexamination Certificate

active

06265505

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a catalyst system of a Group 15 containing transition metal catalyst compound and a Lewis acid aluminum containing activator 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 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 system.
SUMMARY OF THE INVENTION
This invention provides for a catalyst system and for its use in polymerizing process.
In one embodiment, the invention is directed to a catalyst system of a Group 15 containing transition metal catalyst compound and a Lewis acid activator and to its use in the polymerization of olefin(s).
In another embodiment, the invention is directed to a catalyst system of a Group 15 containing bidentate or tridentate ligated transition metal catalyst compound and a Lewis acid aluminum containing activator to its use in the polymerization of olefin(s).
In another embodiment, the invention is directed to a catalyst system having a 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, and a Lewis acid aluminum containing activator, and to its use in the polymerization of olefin(s).
In still another embodiment, the invention is directed to a method for supporting the multidentate metal based catalyst 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 supported catalyst systems discussed above.
DETAILED DESCRIPTION OF THE INVENTION
Introduction
It has been found that catalyst systems of a Group 15 containing transition metal catalyst compound and a Lewis acid aluminum containing activators exhibit commercially acceptable productivity with excellent operability. Also, in particular the catalyst system of the invention is supportable on a support material, preferably for use in a slurry or gas phase polymerization process.
Group 15 Containing Metal Catalyst Compound and Catalyst 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 phosphorous, 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, and most preferably an alkyl. In a most preferred embodiment, at least one X is a substituted hydrocarbon group, preferably a substituted alkyl group having more than 6 carbon atoms, more preferably an aryl substituted alkyl group and most preferably a benzyl group.
y is 0 or 1 (when y is 0 group L′ is absent);
n is the oxidation state of M, preferably +2, +3, +4 or +5 and more preferably +4;
m is the formal charge of the YZL or the YZL′ ligand, preferably 0, −1, −2 or −3, and more preferably −2;
L is a Group 15 or 16 element, preferably nitrogen;
L′ is a Group 15 or 16 element or Group 14 containing gro

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