Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
1999-12-22
2003-02-25
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S119000, C502S129000, C526S135000, C526S160000, C526S943000
Reexamination Certificate
active
06524987
ABSTRACT:
FIELD OF THE INVENTION
This invention is related to the field of organometal catalyst compositions.
BACKGROUND OF THE INVENTION
The production of polymers is a multi-billion dollar business. This business produces billions of pounds of polymers each year. Millions of dollars have been spent on developing technologies that can add value to this business.
One of these technologies is called metallocene catalyst technology. Metallocene catalysts have been known since about 1958. However, their low productivity did not allow them to be commercialized. About 1974, it was discovered that contacting one part water with one part trimethylaluminum to form methyl aluminoxane, and then contacting such methyl aluminoxane with a metallocene compound, formed a metallocene catalyst that had greater activity. However, it was soon realized that large amounts of expensive methyl aluminoxane were needed to form an active metallocene catalyst. This has been a significant impediment to the commercialization of metallocene catalysts.
Fluoro-organo borate compounds have been used in place of large amounts of methyl aluminoxane. However, this is not satisfactory, since such borate compounds are very sensitive to poisons and decomposition, and can also be very expensive.
It should also be noted that having a heterogeneous catalyst is important. This is because heterogeneous catalysts are required for most modern commercial polymerization processes. Furthermore, heterogeneous catalysts can lead to the formation of substantially uniform polymer particles that have a high bulk density. These types of substantially uniform particles are desirable because they improve the efficiency of polymer production and transportation. Efforts have been made to produce heterogeneous metallocene catalysts; however, these catalysts have not been entirely satisfactory.
Bridged fluorenyl zirconium metallocenes hold a special place in the development of loop-slurry polyethylene technology. Such compounds are known for their excellent ability to incorporate hexene efficiently, which is important in a loop-slurry process. They also are capable of producing very high molecular weight polymer,which is difficult for bis-cyclopentadienyl zirconium species, or even for bis-indenyl zirconium species. Some, notably [2-(&eegr;
5
-cyclopentadienyl)-2-(&eegr;
5
-fluoren-9-yl)hex-5-ene]zirconium(IV) dichloride, produce exceptionally transparent and glossy films and other manufactures. Bridged fluorenyl zirconium metallocenes are activated well enough by methyl aluminoxanes (MAO), but unfortunately MAO is expensive and in the liquid state tends to cause fouling in the reactor.
An object of this invention is to provide a process that produces a catalyst composition that can be used to polymerize at least one monomer to produce a polymer.
Another object of this invention is to provide the catalyst composition.
Another object of this invention is to provide a process comprising contacting at least one monomer and the catalyst composition under polymerization conditions to produce the polymer.
Another object of this invention is to provide an article that comprises the polymer produced with the catalyst composition of this invention.
SUMMARY OF THE INVENTION
In accordance with one embodiment of this invention, a process to produce a catalyst composition is provided. The process comprises (or optionally, “consists essentially of,” or “consists of”):
1) contacting at least one organometal compound and at least one first organoaluminum compound to produce an organometal/organoalurinumn mixture;
wherein the organometal compound has the following general formula:
(X
1
)(X
2
)(X
3
)(X
4
)M
1
wherein M
1
is selected from the group consisting of titanium, zirconium, and hafnium;
wherein (X
1
) and (X
2
) are cyclopentadienyl derivatives and at least one is a fluorenyl or substituted fluorenyl;
wherein cyclopentadienyl derivatives are selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls;
wherein substituents on the substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls of(X
1
) and (X
2
) are selected from the group consisting of aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, silyl groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups, oxygen groups, silicon, phosphorus, boron, germanium, and hydrogen;
wherein (X
1
) and (X
2
) are connected by a bridge having one or two atoms between (X
1
) and (X
2
); and further wherein the one or two atoms of the bridge can contain substituents;
wherein (X
3
) and (X
4
) are independently selected from the group consisting of halides, aliphatic groups, substituted aliphatic groups, cyclic groups, substituted cyclic groups, combinations of aliphatic groups and cyclic groups, combinations of substituted aliphatic groups and cyclic groups, combinations of aliphatic groups and substituted cyclic groups, combinations of substituted aliphatic groups and substituted cyclic groups, amido groups, substituted amido groups, phosphido groups, substituted phosphido groups, alkyloxide groups, substituted alkyloxide groups, aryloxide groups, substituted aryloxide groups, organometallic groups, and substituted organometallic groups; and
wherein the first organoaluminum compound is selected from the group consisting of triethyl aluminum, tripropyl aluminum, and tri-n-butyl aluminum;
2) contacting the organometal/organoaluminum mixture with a treated solid oxide compound and optionally, at least one second organoaluminum compound;
wherein the second organoaluminum compound is added in a reactor, and is represented by the following formula:
Al(X
5
)
n
(X
6
)
3−n
wherein (X
5
) is a hydrocarbyl having from 1 to about 20 carbon atoms;
wherein (X
6
) is a halide, hydride, or alkoxide; and
wherein “n” is a number from 1 to 3 inclusive; and;
wherein the treated solid oxide compound is produced by a process comprising: a) contacting at least one solid oxide compound with at least one electron-withdrawing anion source compound; b) optionally, also contacting the solid oxide compound with at least one metal salt compound; and c) calcining the solid oxide compound before, during, or after contacting the electron-withdrawing anion source compound or metal salt compound to produce the treated solid oxide compound.
In accordance with a second embodiment of this invention, a process is provided comprising contacting at least one monomer and the catalyst composition under polymerization conditions to produce a polymer.
In accordance with a third embodiment of this invention, an article is provided. The article comprises the polymer produced in accordance with this invention.
These objects, and other objects, will become more apparent to those with ordinary skill in the art after reading this disclosure.
DETAILED DESCRIPTION OF THE INVENTION
A process to produce a catalyst composition is provided. The process comprises contacting at least one organometal compound and at least one first organoaluminum compound to produce an organometal/organoaluminum mixture. Then, contacting the organometal/organoaluminum mixture with a treated solid oxide compound and optionally, at least one second organoaluminum compound to produce the catalyst composition.
The organometal compound utilized in this invention has the following general formula:
(X
1
)(X
2
)(X
3
)(X
4
)M
1
M
1
is selected from the group consisting of titanium, zirconium, and hafnium. Preferably, M
1
is zirconium.
(X
1
) and (X
2
) are cyclopentadienyl derivatives and at least one is a fluorenyl or substituted fluorenyl. Cyclopentadienyl derivatives are selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls. Preferably, (X
1
) or (X
2
) is cyclopentadienyl.
Substituents on the substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls of (X
1
) and
Benham Elizabeth A.
Collins Kathy S.
Eaton Anthony P.
Farmer Kenneth R.
Hawley Gil R.
Bell Mark L.
Pasterczyk J.
Phillips Petroleum Company
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