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
2000-02-11
2003-06-10
Wood, Elizabeth (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...
C502S107000, C502S113000, C502S129000, C502S227000
Reexamination Certificate
active
06576583
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 organic borate compounds have been used in place of large amounts of methyl aluminoxane. However, this is not satisfactory, since these 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.
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.
These objects, and other objects, will become more apparent to those with ordinary skill in the art after reading this disclosure.
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”) contacting at least one organometal compound, at least one organoaluminum compound, and at least one solid to produce the catalyst composition,
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
) is independently 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
) 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, silicon, phosphorus, boron, germanium, and hydrogen;
wherein at least one substituent on (X
1
) can be a bridging group which connects (X
1
) and (X
2
);
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;
wherein (X
2
) is selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, substituted fluorenyls, 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;
wherein substituents on (X
2
) are selected from the group consisting of aliphatic groups, cyclic groups, combinations of aliphatic groups and cyclic groups, silyl groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups, silicon, phosphorus, boron, germanium, and hydrogen;
wherein at least one substituent on (X
2
) can be a bridging group which connects (X
1
) and (X
2
);
wherein the organoaluminum compound has the following general formula:
Al(X
5
)
n
(X
6
)
3−n
wherein (X
5
) is a hydrocarbyl having from 1-20 carbon atoms;
wherein (X
6
) is a halide, hydride, or alkoxide;
wherein the solid is selected from the group consisting of titanium tetrafluoride, zirconium tetrafluoride, and a treated solid oxide compound;
wherein the treated solid oxide compound comprises a solid oxide compound having titanium tetrafluoride or zirconium tetrafluoride deposited on the surface of the solid oxide compound; and
wherein the solid oxide comprises oxygen and at least one element selected from the group consisting of groups 2-9 and 11-17 of the Periodic Table of Elements, including lanthanides and actinides.
In accordance with another 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 another embodiment of this invention, an article is provided. The article comprises the polymer produced in accordance with this invention.
DETAILED DESCRIPTION OF THE INVENTION
A process to produce a catalyst composition is provided. The process comprises contacting at least one organometal compound, at least one organoaluminum compound, and at least one solid.
Organometal compounds used in this invention have the following general formula:
(X
1
)(X
2
)(X
3
)(X
4
)M
1
In this formula, M
1
is selected from the group consisting of titanium, zirconium, and hafnium. Currently, it is most preferred when M
1
is zirconium.
In this formula, (X
1
) is independently selected from the group consisting of (hereafter “Group OMC-I”) cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, such as, for example, tetrahydroindenyls, and substituted fluorenyls, such as, for example, octahydrofluorenyls.
Substituents on the substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls of (X
1
) can be selected independently 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, silicon, phosphorus, boron, germanium, and hydrogen, as long as these groups do not to substantially, and adversely, affect the polymerization activity of the catalyst composition.
Suitable examples of aliphatic groups are hydrocarbyls, such as, for example, paraffins and olefins. Suitable examples of cyclic groups are cycloparaffins, cycloolefins, cyc
Benham Elizabeth A.
Collins Kathy S.
Hawley Gil R.
Jensen Michael D.
Johnson Marvin M.
Pasterczyk J.
Phillips Petroleum Company
Wood Elizabeth
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