Organometal catalyst compositions

Details Organometal catalyst compositions Organometal catalyst compositions

1999-10-27

2003-04-15

Wu, David W. (Department: 1713)

Catalyst, solid sorbent, or support therefor: product or process

Zeolite or clay, including gallium analogs

Clay

C502S102000, C502S103000, C502S104000, C502S117000, C502S132000, C502S134000, C502S152000, C526S097000, C526S114000, C526S116000, C526S128000, C526S160000, C526S348000, C526S943000

Reexamination Certificate

active

06548441

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 1960. However, their low productivity did not allow them to be commercialized. About 1975, 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.
Borate compounds have been used in place of large amounts of methyl aluminoxane. However, this is not satisfactory, since 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 uniformed 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.
Therefore, the inventors provide this invention to help solve these problems.
SUMMARY OF THE INVENTION
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 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.
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 an organometal compound, an organoaluminum compound, and a treated solid oxide compound to produce the catalyst composition;
wherein the organometal compound has the following general formula:
(X
1
)(X
2
)(X
3
)(X4)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 “n” is a number from 1 to 3 inclusive; and
wherein the treated solid oxide compound comprises nickel, a halogen, and a solid oxide compound;
wherein the halogen is selected from the group consisting of chlorine and bromine;
wherein the solid oxide compound is selected from the group consisting of alumina, aluminophosphate, aluminosilicate, and mixtures thereof.
In accordance with another embodiment of this invention, a process is provided comprising contacting at least one monomer and the catalyst composition under polymerization condition 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.
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
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 substantially, and adversely, affect the polymerization activity of the composition.
Suitable examples of aliphatic groups are hydrocarbyls, such as, for example, paraffins and olefins. Suitable examples of cyclic groups are cycloparaffms, cycloolefins, cycloacetylenes, and arenes. Substituted silyl groups include, but are not limited to, alkylsilyl groups where each alkyl group contains from 1 to about 12 carbon a toms, arylsily

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