Polymerization catalysts

Details Polymerization catalysts Polymerization catalysts

2000-08-16

2003-12-23

Choi, Ling-Siu (Department: 1713)

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

Solid sorbent

Aluminum containing

C502S152000, C502S104000, C502S102000, C502S103000, C502S117000, C502S118000, C502S119000, C502S132000, C526S160000, C526S943000, C526S348000, C526S130000, C526S154000, C526S129000

Reexamination Certificate

active

06667274

ABSTRACT:

FIELD OF THE INVENTION
This invention is related to the field of catalyst compositions that can be used to polymerize at least one alpha olefin to produce a polymer.
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 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 for producing a catalyst precursor for use in a catalyst composition.
Another object is to provide the catalyst precursor.
Another object of this invention is to provide a process for producing the catalyst composition.
Another object of this invention is to provide the catalyst composition.
Another object of this invention is to provide a process of using the catalyst composition to polymerize at least one alpha olefin to produce a polymer.
Another object of this invention is to provide the polymer produced by the catalyst composition.
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 precursor is provided. The process consists essentially of contacting at least one treated solid oxide compound and at least one alpha olefin;
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 the metal salt compound to produce the treated solid oxide compound.
In accordance with another embodiment of this invention, the catalyst precursor is provided.
In accordance with another embodiment of this invention, a process for producing a catalyst composition is provided. The process comprises:
1) contacting the catalyst precursor with at least one organometal compound and at least one organoaluminum compound 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
) and (X
2
) are 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
) 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, silicon, phosphorus, boron, germanium, and hydrogen;
wherein at least one substituent on (X
1
) and (X
2
) is 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; and
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.
In accordance with another embodiment of this invention, a process is provided to produce a catalyst composition. The process comprising simultaneously contacting at least one treated solid oxide compound, at least one organometal compound, at least one organaluminum compound, and at least one alpha olefin to produce the catalyst composition.
In accordance with another embodiment of this invention, a process is provided to produce a polymer. The process comprises contacting the catalyst composition with at least one additional alpha olefin in a polymerization zone under polymerization conditions to produce the polymer.
In accordance with another embodiment of this invention, a process is provided to produce a polymer. The process comprises simultaneously contacting an organometal compound, an organoaluminum compound, a treated solid oxide compound and at least one alpha olefin under polymerization conditions to produce a polymer. The organometal compound, the organoaluminum compound and the treated solid oxide compound are as described in the previous embodiment.
In accordance with another embodiment of this invention, a polymer is provided.
DETAILED DESCRIPTION OF THE INVENTION
In a first embodiment of this invention, a process to produce a catalyst precursor is provided. The process consists essentially of contacting at least one treated solid oxide compound and at least one alpha olefin.
Treated solid oxide compounds are compounds that have had their Lewis acidity increased. The treated solid oxide compound can be produced by a process comprising contacting at least one solid oxide compound with at least one electron-withdrawing anion source to form an anion-containing solid oxide compound. The solid oxide compound is calcined either prior to, during, or after contacting with the electron-withdrawing anion source. Calcining is discussed later in this disclosure.
Generally, the specific surface area of the solid oxide compound after calcining at 500° C. is from about 100 to about 1000 m
2
/g, preferably, from about 200 to about 800 m
2
/g, and most preferably, from 250 to 600 m
2
/g.
The specific pore volume of the solid oxide compound is typically greater than about 0.5 cc/g, preferably, greater than about 0.8 cc/g, and most preferably, greater than 1.0 cc/g.
It is preferred when the treated solid oxide compound comprises oxygen and at least one element selected from the group consisting of groups IIA-VIIIA and IB-VIIB of the Periodic Table of Elements, including lanth

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