Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymerizing in tubular or loop reactor
Reexamination Certificate
2000-04-28
2001-11-13
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymerizing in tubular or loop reactor
C526S095000, C526S099000, C526S159000, C526S348200, C526S348400, C526S348500
Reexamination Certificate
active
06316553
ABSTRACT:
FIELD OF THE INVENTION
This invention is related to the field of compositions that can be used to polymerize monomers into at least one 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 1960, however, their low productivity did not allow them to be commercialized. About 1975, it was discovered that contacting one part water with two parts trimethylaluminum to form methyl aluminoxane, and then contacting such ethyl 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 use 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 solve these problems.
SUMMARY OF THE INVENTION
An object of this invention is to provide a process that produces a composition that can be used to polymerize monomers into at least one polymer.
Another object of this invention is to provide said composition.
Another object of this invention is to provide a process to polymerize monomers into at least one polymer using said composition.
Another object of this invention is to provide a manufacture that comprises at least one said polymer.
Another object of this invention is to provide a machine that comprises at least one said manufacture.
In accordance with one embodiment of this invention, a process to produce a composition of matter is provided. Said process comprises (or optionally, consists essentially of, or consists of) contacting an organometal compound, a treated solid oxide compound, and an organoaluminum compound to produce said composition, wherein said composition consists essentially of (or optionally, consists of) a post-contacted organometal compound, a post-contacted treated solid oxide compound, and optionally, a post-contacted organoaluminum compound.
In accordance with another embodiment of this invention, a composition of matter is provided. Said composition consists essentially of a post-contacted organometal compound, a post-contacted treated solid oxide compound, and optionally, a post-contacted organoaluminum compound.
In accordance with another embodiment of this invention, a process to polymerize monomers into at least one polymer using said composition is provided. Said process comprises contacting said composition with monomers.
In accordance with another embodiment of this invention a manufacture is provided. Said manufacture comprises at least one said polymer.
In accordance with another embodiment of this invention a machine is provided. Said machine comprises at least two said manufactures.
These objects, and other objects, will become more apparent to those with ordinary skill in the art after reading this disclosure.
It should be noted that the phrase “consisting essentially of” means that the only other items (such as, for example, process steps, and other compounds) included within the scope of the claims are those items that do not materially affect the basic and novel characteristics of the claimed invention.
It should also be noted that the phrase “consisting of” means that the no other items (such as, for example, process steps, and other compounds) are included within the scope of the claims, except items that are impurities ordinarily associated with a composition, or items that are process steps ordinarily associated with a process.
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
FORMULA ONE
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.
The substituents on the substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls, can be aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and organometallic groups, as long as these groups do not substantially, and adversely, affect the polymerization activity of the composition. Additionally, hydrogen can be a substituent.
Suitable examples of aliphatic groups are hydrocarbyls, such as, for example, paraffins and olefins. Suitable examples of cyclic groups are cycloparaffins, cycloolefins, cycloacetylenes, and arenes. Additionally, alkylsilyl groups where each alkyl contains 1-12 carbon atoms, alkyl halide groups where each alkyl contains 1-12 carbon atoms, or halides, can also be used.
Suitable examples of such substituents are methyl, ethyl, propyl, butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl, chloro, bromo, and iodo.
In this formula (X
3
) and (X
4
) are independently selected from the group consisting of (hereafter “Group OMC-II”) halides, aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and organometallic groups, 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 cycloparaffins, cycloolefins, cycloacetylenes, and arenes. Currently, it is preferred when (X
3
) and (X
4
) are selected from the group consisting of halides and hydrocarbyls, where such hydrocarbyls have from 1 to 10 carbon atoms. However, it is most preferred when (X
3
) and (X
4
) are selected from the group consisting of fluoro, chloro, and methyl.
In this formula, (X
2
) can be selected from either Group OMC-I or Group OMC-II.
When (X
2
) is selected from Group OMC-I, it should be noted that (X
1
) and (X
2
) can be joined with a bridging group, such as, for example, aliphatic bridging groups, cyclic bridging groups, combinations of aliphatic and cyclic bridging groups, and organometallic bridging groups, as long as the bridging group does not substantially, and adversely, affect the polymerization activity of the composition.
Suitable examples of aliphatic bridging groups are hydrocarbyls, such as, for example, paraffins and olefins. Suitable examples of cyclic bridging groups are cycloparaffins, cycloolefins, cycloacetylenes, and arenes. Additionally, it should be noted that silicon and germanium are also good bridging units.
Various processes are known to make these compositions. See, for example, U.S. Pat. Nos. 4,939,217; 5,210,352; 5,436,305; 5,401,817; 5,631,335, 5,571,880; 5,191,132; 5,480,848; 5,399,636; 5,565,592; 5,347,026; 5,594,078; 5,498,581; 5,496,781; 5,563,284; 5,554,795; 5,
Benham Elizabeth A.
Collins Kathy S.
Hawley Gil R.
Jensen Michael D.
Johnson Marvin M.
Cheung William K.
Owen Polly C.
Phillips Petroleum Company
Wu David W.
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