Title:

Polymerization process using a supported, treated catalyst system

Document Type and Number:

United States Patent 7410926

Abstract:

The present invention relates to a supported, treated catalyst system and its use in a process for polymerizing olefin(s). More particularly, it provides a supported, treated catalyst system produced by a process comprising the steps of: (a) forming a supported bimetallic catalyst system comprising a first catalyst component and a metallocene catalyst compound; and (b) contacting the supported bimetallic catalyst system of (a) with at least one methylalumoxane-activatable compound.

Inventors:

Kao, Sun-chueh (Hillsborough, NJ, US)

Plaque It!

FIELD OF THE INVENTION

The present invention relates to a supported, treated catalyst system and its use in a process for polymerizing olefin(s). In particular, the invention is directed to a supported, treated catalyst system that includes a supported bimetallic catalyst system that has been contacted with at least one methylalumoxane-activatable compound, and polymerization process employing such a supported, treated catalyst system.

BACKGROUND OF THE INVENTION

Advances in polymerization and catalysis have resulted in the ability to produce many new polymers having improved physical and chemical properties useful in a wide variety of superior products and applications. The development of new catalysts has greatly expanded the choice of polymerization processes (solution, slurry, high pressure or gas phase) for producing a particular polymer. Also, advances in polymerization technology have provided more efficient, highly productive and economically enhanced processes. Especially illustrative of these advances is the development of the technology field utilizing metallocene catalyst systems.

As with any new technology field, particularly in the polyolefins industry, a small savings in cost often determines whether a commercial endeavor is even feasible. This aspect of the metallocene technology field is evident by the number of participants in the industry seeking new ways to reduce cost. In particular, there has been tremendous focus in the industry on developing new and improved metallocene catalyst systems. Some have focused on designing the catalyst systems to produce new polymers, others on improved operability, and many more on improving catalyst productivity. The productivity of a catalyst, that is, the amount of polymer produced per gram of the catalyst per hour, usually is the key economic factor that can make or break a new commercial development in the polyolefins industry.

From the early stages in the metallocene technology field, beginning with the discovery of the utility of alumoxane as a cocatalyst in the early 1980's, to the discovery of substitutions on the ligands of the metallocene compounds, through the development of non-coordinating anions, and today with the ever-increasing number of new metallocene compounds, catalyst productivity has been a primary focus.

A need still exists for higher productivity catalyst systems capable of providing the efficiencies necessary for implementing commercial polyolefin processes. Further, it has been found that conventional olefin polymerization processes that employ catalyst systems that use methylalumoxane as an activator often fail to efficiently utilize all the methylalumoxane present in the catalyst system. This is problematic because methylalumoxane represents a significant cost factor in the catalyst system. Thus, it would be highly advantageous to have a polymerization process and catalyst system capable of producing polyolefins with improved catalyst productivities and improved methylalumoxane efficiency.

SUMMARY OF THE INVENTION

In one exemplary embodiment, the present invention provides a process for polymerizing olefins by contacting, in a reactor: (a) ethylene and at least one comonomer selected from the group consisting of C4 to C8 alpha olefins; and (b) a supported, treated catalyst system that includes a first catalyst component, a second catalyst component, and at least one methylalumoxane-activatable compound.

In another exemplary embodiment, a supported, treated catalyst system is produced by a process comprising the steps of: (a) forming a supported bimetallic catalyst system comprising a first catalyst component and a second catalyst component; and (b) contacting the supported bimetallic catalyst system with at least one methylalumoxane-activatable compound.

DESCRIPTION OF THE DRAWINGS

A more complete understanding of the present disclosure and advantages thereof may be acquired by referring to the following description taken in conjunction with the accompanying drawings, wherein:

FIG. 1 illustrates a molecular weight distribution for an exemplary supported bimetallic catalyst composition.

FIG. 2 illustrates a molecular weight distribution for an exemplary supported, treated catalyst system of the present invention.

FIG. 3 illustrates a molecular weight distribution for an exemplary supported, treated catalyst system of the present invention.

FIG. 4 illustrates a molecular weight distribution for an exemplary supported, treated catalyst system of the present invention.

FIG. 5 illustrates a molecular weight distribution for an exemplary supported, treated catalyst system of the present invention.

FIG. 6 illustrates a molecular weight distribution for an exemplary supported, treated catalyst system of the present invention.

DETAILED DESCRIPTION

General Definitions

As used herein, in reference to Periodic Table “Groups” of Elements, the “new” numbering scheme for the Periodic Table Groups is used, as in the CRC HANDBOOK OF CHEMISTRY AND PHYSICS (David R. Lide ed., CRC Press 81^sted. 2000).

As used herein, the phrase “catalyst system” includes at least one “catalyst component” and at least one “activator,” both of which are described further herein. The catalyst system may also include other components (such as supports, for example), and is not limited to the catalyst component and/or activator alone, or in combination. The catalyst system may include any number of catalyst components, in any combination as described herein, and may also include any activator in any combination as described herein. In one embodiment of the present invention, a “supported, treated catalyst system” is provided that includes a “bimetallic catalyst system” that has been contacted with at least one compound that can be activated by methylalumoxane (“MAO-activatable compound”).

As used herein, the term “bimetallic catalyst” or “bimetallic catalyst system” refers to two or more catalyst components that may be used in combination with at least one activator and a support material.

As used herein, the phrase “catalyst compound” includes any compound that, once appropriately activated, is capable of catalyzing the polymerization or oligomerization of olefins, the catalyst compound including at least one Group 3 to Group 12 atom, and optionally at least one leaving group bound thereto.

As used herein, the phrase “leaving group” refers to one or more chemical moieties bound to the metal center of the catalyst component, which can be abstracted from the catalyst component by an activator, thus producing a species active towards olefin polymerization or oligomerization. The activator is described further below.

As used herein, the term “substituted” means that the group following that term possesses at least one moiety in place of one or more hydrogens in any position, which moieties are selected from such groups as halogen radicals (e.g., Cl, F, Br), hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, C₁to C₁₀alkyl groups, C₂to C₁₀alkenyl groups, and combinations thereof. Examples of substituted alkyls and aryls include, but are not limited to, acyl radicals, alkylamino radical, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- and dialkyl-carbomoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals, and combinations thereof.

As used herein, structural formulas are employed in manners that are commonly understood in the chemical arts. For example, the lines (“- - ”) that are used to represent associations between a metal atom (“M,” Group 3 to Group 12 atoms) and a ligand or ligand atom (e.g., cyclopentadienyl, nitrogen, oxygen, halogen ions, alkyl, etc.), as well as the phrases “associated with,” “bonded to” and “bonding,” are not limited to representing a certain type of chemical bond; rather, these lines and phrases are meant to represent a “chemical bond” in general. As used herein, the phrase “chemical bond” is defined as an attractive force between atoms that is strong enough to permit the combined aggregate to function as a unit, or “compound.”

A certain stereochemistry for a given structure or part of a structure should not be implied unless so stated for a given structure or apparent by use of commonly used bonding symbols, such as by dashed lines and/or heavy lines.

Unless stated otherwise, no embodiment of the present invention is herein limited to the oxidation state of the metal atom “M” as defined below in the individual descriptions and examples that follow. The ligation of the metal atom “M” is such that the compounds described herein are neutral, unless otherwise indicated.

As used herein, the term “bimodal,” when used to describe a polymer or polymer composition (e.g., polyolefins such as polypropylene or polyethylene, or other homopolymers, copolymers or terpolymers) means “bimodal molecular weight distribution,” which is understood as having the broadest definition persons in the pertinent art have given that term as reflected in printed publications and issued patents. For example, a single composition that includes polyolefins with at least one identifiable high molecular weight distribution and polyolefins with at least one identifiable low molecular weight distribution is considered to be a “bimodal” polyolefin, as that term is used herein. In a particular embodiment, other than having different molecular weights, the high molecular weight polyolefin and the low molecular weight polyolefin may be essentially the same type of polymer, for example, polyethylene.

As used herein, the term “productivity” means the weight of polymer produced per weight of the catalyst used in the polymerization process per time period (e.g., grams polymer/(gram catalyst·hour).

As used herein, the term “dehydrated” is understood as having the broadest definition that persons in the pertinent art have given that term in describing catalyst support materials (for example, silica) as reflected in printed publications and issued patents, and includes any material (for example, a support particle) from which a majority of the contained/adsorbed water has been removed.

As used herein, the term “MAO efficiency” refers to the grams of polyethylene produced per mmol aluminum (contributed by MAO) present on the supported (or supported, treated) catalyst per hour when the supported (or supported, treated) catalyst system is used in a polymerization process.

Bimetallic Catalyst

As used herein, the term “supported bimetallic catalyst” or “supported bimetallic catalyst composition” refers to a bimetallic catalyst system as used in combination with a support material, wherein one or more of the components that make up the bimetallic catalyst system may be bound to the support. In a particular embodiment, the bimetallic catalyst used in accordance with the present invention includes two catalyst components. In a more particular embodiment, the bimetallic catalyst includes a “first catalyst component” and a “second catalyst component.”

As used herein, the term “first catalyst component” refers to any catalyst component other than the second catalyst component. In certain exemplary embodiments, the first catalyst component is a non-metallocene catalyst component, examples of which include, but are not limited to, titanium or vanadium based Ziegler-Natta catalyst compounds as described further herein. In an exemplary embodiment, the first catalyst component is titanium tetrachloride.

As used herein, the term “non-metallocene catalyst component” refers to any catalyst component that is neither a metallocene nor one of the metallocene-type catalyst compounds identified below.

As used herein, the term “second catalyst component” refers to any catalyst component that is different from a first catalyst component. In an exemplary embodiment, the second catalyst component is a metallocene catalyst component.

In an exemplary embodiment, each different catalyst compound that comprises the bimetallic catalyst resides, or is supported, on a single type of support such that, on average, each particle of support material includes both the first and second catalyst components. In another exemplary embodiment, the first catalyst component is supported separately from the second catalyst component such that, on average, any given particle of support material comprises only the first or the second catalyst component. In this later embodiment, each supported catalyst component may be introduced into the polymerization reactor sequentially in any order, alternately in parts, or simultaneously.

In a particular embodiment, the first catalyst component includes a titanium non-metallocene catalyst component, from which a higher molecular weight resin (e.g., >ca 100,000 amu) can be produced. In a particular embodiment, the second catalyst component includes a metallocene component, from which a lower molecular weight resin (e.g., <ca 100,000 amu) can be produced. Accordingly, when such bimetallic catalyst is included in the supported, treated catalyst systems of the present invention, polymerization in the presence of such supported, treated catalyst system may provide a bimodal polyolefin composition that includes a low molecular weight component and a high molecular weight component.

In one exemplary embodiment, an “enhanced silica” is prepared as described herein and constitutes the support for the bimetallic catalyst. In an exemplary embodiment, the first catalyst component is a non-metallocene compound that is first combined with the enhanced silica, to provide a supported non-metallocene composition that is combined with the second catalyst component.

Various methods of affixing two different catalyst components (albeit a different combination of catalysts) to a support can be used. One procedure for preparing a supported bimetallic catalyst can include providing a supported first catalyst component, contacting a slurry that includes the first catalyst component in a non-polar hydrocarbon with a solution that includes the second catalyst component, which may also include an activator, drying the resulting product that includes the first and second catalyst components, and recovering a supported bimetallic catalyst composition. The present invention is not limited to any particular method of affixing the catalyst components to the support.

First Catalyst Component

As noted above, exemplary embodiments of the bimetallic catalyst composition useful in the supported, treated catalyst systems of the present invention may include a first catalyst component, which is, or may include, a non-metallocene compound. However, it is contemplated that for certain applications the first catalyst component may alternatively be a metallocene compound, or even one of the metallocene-type catalyst compounds identified below that is different in structure from the second catalyst component as described herein. In a particular embodiment, the first catalyst component is a Ziegler-Natta catalyst compound. Ziegler-Natta catalyst components are well known in the art and described by, for example, ZIEGLER CATALYSTS 363-386 (G. Fink, R. Mulhaupt and H. H. Brintzinger, eds., Springer-Verlag 1995). Examples of such catalysts include those comprising TiCl₄and other such transition metal oxides and chlorides.

The first catalyst component is combined with a support material, in one exemplary embodiment, either with, or without, the second catalyst component. The first catalyst component can be combined with, placed on, or otherwise affixed to a support in a variety of ways. In one of those ways, a slurry of the support in a suitable non-polar hydrocarbon diluent is contacted with an organomagnesium compound, which then dissolves in the non-polar hydrocarbon diluent of the slurry to form a solution from which the organomagnesium compound is then deposited onto the carrier. The organomagnesium compound can be represented by the formula RMgR′, where R′ and R are the same or different C₂-C₁₂alkyl groups, or C₄-C₁₀alkyl groups, or C₄-C₈alkyl groups. In one exemplary embodiment, the organomagnesium compound is dibutyl magnesium. In one exemplary embodiment, the amount of organomagnesium compound included in the silica slurry is essentially only that which will be deposited, physically or chemically, onto the support (for example, being bound to the hydroxyl groups on the support) and essentially no more than that amount, as any excess organomagnesium compound may cause undesirable side reactions. Routine experimentation can be used to determine the optimum amount of organomagnesium compound. For example, the organomagnesium compound can be added to the slurry while stirring the slurry, until the organomagnesium compound is detected in the support solvent. Alternatively, the organomagnesium compound can be added in excess of the amount that is deposited onto the support, in which case any undeposited excess amount can be removed by filtration and washing. The amount of organomagnesium compound (moles) based on the amount of dehydrated silica (grams) generally ranges from 0.2 mmol/gram to 2 mmol/gram, in one exemplary embodiment.

Optionally, the organomagnesium compound-treated slurry may be contacted with an electron donor, such as tetraethylorthosiloxane (TEOS) or an organic alcohol R″OH, where R″ is a C₁-C₁₂alkyl group, or a C₁to C₈alkyl group, or a C₂to C₄alkyl group. In a particular embodiment, R″OH is n-butanol. The amount of alcohol used may be an amount effective to provide an R″OH:Mg mol/mol ratio of from 0.2 to 1.5, or from 0.4 to 1.2, or from 0.6 to 1.1, or from 0.9 to 1.0.

In an exemplary embodiment, the organomagnesium-and-alcohol-treated slurry is contacted with a non-metallocene transition metal compound. Suitable non-metallocene transition metal compounds are, for example, compounds of Group 4 and 5 metals that are soluble in the non-polar hydrocarbon used to form the silica slurry. Suitable non-metallocene transition metal compounds include, for example, titanium and vanadium halides, oxyhalides or alkoxyhalides, such as titanium tetrachloride (TiCl₄), vanadium tetrachloride (VCl₄) and vanadium oxytrichloride (VOCl₃), and titanium and vanadium alkoxides, wherein the alkoxide moiety has a branched or unbranched alkyl group of 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Mixtures of such transition metal compounds also may be used. The amount of non-metallocene transition metal compound used is sufficient to give a molar ratio of transition metal to magnesium of from 0.3 to 1.5, or from 0.5 to 0.8 in a particular exemplary embodiment. The diluent can then be removed in a conventional manner, such as by evaporation or filtering, to obtain the dry, supported first catalyst component.

The first and second catalyst components may be contacted with the support in any order. In a particular exemplary embodiment of the invention, the first catalyst component is reacted first with the support as described above, then this supported first catalyst component is contacted with a second catalyst component.

Second Catalyst Component

As referred to herein, the term “second catalyst component” will be understood to refer to any catalyst component that is different from a first catalyst component. In an exemplary embodiment, the second catalyst component is a metallocene catalyst component.

Metallocene catalyst compounds are generally described throughout in 1 & 2 METALLOCENE-BASED POLYOLEFINS (John Scheirs & W. Kaminsky eds., John Wiley & Sons, Ltd. 2000); G. G. Hlatky in 181 COORDINATION CHEM. REV. 243-296 (1999) and in particular, for use in the synthesis of polyethylene, in 1 METALLOCENE-BASED POLYOLEFINS 261-377 (2000). The metallocene catalyst compounds as described herein include “half sandwich” and “full sandwich” compounds having one or more Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to at least one Group 3 to Group 12 metal atom, and one or more leaving group(s) bound to the at least one Group 3 to Group 12 metal atom. Hereinafter, these compounds will be referred to as “metallocenes” or “metallocene catalyst components.” The metallocene catalyst component is supported on a support material, in a particular embodiment that is described further below, and may be supported with, or without, the first catalyst component. In a particular exemplary embodiment, the metallocene catalyst component is supported with the first catalyst component.

The Cp ligands are typically p-bonded and/or fused ring(s) or ring systems. The ring(s) or ring system(s) typically comprise atoms selected from the group consisting of Groups 13 to 16 atoms, and in a particular exemplary embodiment, the atoms that make up the Cp ligands are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum and combinations thereof, wherein carbon makes up at least 50% of the ring members. In a more particular exemplary embodiment, the Cp ligand(s) are selected from the group consisting of substituted and unsubstituted cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, non-limiting examples of which include cyclopentadienyl, indenyl, fluorenyl and other structures. Further non-limiting examples of such ligands include cyclopentadienyl, cyclopentaphenanthrenyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7H-dibenzofluorenyl, indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or “H₄Ind”), substituted versions thereof, and heterocyclic versions thereof. In a particular exemplary embodiment, the metallocenes useful in the present invention are selected from those including one or two (two in a more particular exemplary embodiment) of the same or different Cp rings selected from the group consisting of cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, and substituted versions thereof.

The metal atom “M” of the metallocene catalyst compound may be selected from the group consisting of Groups 3 through 12 atoms and lanthanide Group atoms in one exemplary embodiment; and selected from the group consisting of Groups 3 through 10 atoms in a more particular exemplary embodiment; and selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni in yet a more particular embodiment; and selected from the group consisting of Groups 4, 5 and 6 atoms in yet a more particular embodiment, and Ti, Zr, Hf atoms in yet a more particular embodiment, and Zr in still a more particular embodiment. The oxidation state of the metal atom “M” may range from 0 to +7 in one exemplary embodiment; and, in a more particular embodiment, may be +1, +2, +3, +4 or +5; and in yet a more particular embodiment may be +2, +3 or +4. The groups bound to the metal atom “M” are such that the compounds described below in the formulas and structures are electrically neutral, unless otherwise indicated. The Cp ligand(s) form at least one chemical bond with the metal atom M to form the “metallocene catalyst compound.” The Cp ligands are distinct from the leaving groups bound to the catalyst compound in that they are not highly susceptible to substitution/abstraction reactions.

In one exemplary embodiment, the supported bimetallic catalyst includes a metallocene catalyst component represented by the formula (I):
Cp^ACp^BMX_n (I)
wherein M is as described above;

each X is chemically bonded to M;
each Cp group is chemically bonded to M;
and n is an integer from 0 to 4, and either 1 or 2 in a particular embodiment.

The ligands represented by Cp^Aand Cp^Bin formula (I) may be the same or different cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, either or both of which may contain heteroatoms, and either or both of which may be substituted by a group R. In one exemplary embodiment, Cp^Aand Cp^Bare independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.

Independently, each Cp^Aand Cp^Bof formula (I) may be unsubstituted or substituted with any one or combination of substituent groups R. Non-limiting examples of substituent groups R as used in structure (I) as well as ring substituents in structures (Va-d) include substituent groups R selected from the group consisting of hydrogen radicals, alkyls, alkenyls, alkynyls, cycloalkyls, aryls, acyls, aroyls, alkoxys, aryloxys, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos, and combinations thereof. More particular non-limiting examples of alkyl substituent groups R associated with formulae (I) through (V) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groups and the like, including all their isomers, such as, for example, tertiary-butyl, isopropyl, and the like. Other possible radicals include substituted alkyls and aryls such as, for example, fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals, including dimethylboron, for example; and disubstituted Group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine; and Group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide. Other substituent groups R include olefins such as, but not limited to, olefinically unsaturated substituents including vinyl-terminated ligands, for example 3-butenyl, 2-propenyl, 5-hexenyl and the like. In one exemplary embodiment, at least two R groups (two adjacent R groups in a particular exemplary embodiment) are joined to form a ring structure having from 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron and combinations thereof. Also, a substituent R group such as 1-butanyl may form a bonding association to the element M.

Each X in the formula (I) above, and for the formulae/structures (II) through (Va-d) below, is independently selected from the group consisting of: any leaving group, in one exemplary embodiment; halogen ions, hydrides, C₁to C₁₂alkyls, C₂to C₁₂alkenyls, C₆to C₁₂aryls, C₇to C₂₀alkylaryls, C₁to C₁₂alkoxys, C₆to C₁₆aryloxys, C₇to C₁₈alkylaryloxys, C₁to C₁₂fluoroalkyls, C₆to C₁₂fluoroaryls, and C₁to C₁₂heteroatom-containing hydrocarbons and substituted derivatives thereof in a more particular embodiment; hydride, halogen ions, C₁to C₆alkyls, C₂to C₆alkenyls, C₇to C₁₈alkylaryls, C₁to C₆alkoxys, C₆to C₁₄aryloxys, C₇to C₁₆alkylaryloxys, C₁to C₆alkylcarboxylates, C₁to C₆fluorinated alkylcarboxylates, C₆to C₁₂arylcarboxylates, C₇to C₁₈alkylarylcarboxylates, C₁to C₆fluoroalkyls, C₂to C₆fluoroalkenyls, and C₇to C₁₈fluoroalkylaryls in yet a more particular embodiment; hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl, fluoromethyls and fluorophenyls in yet a more particular embodiment; C₁to C₁₂alkyls, C₂to C₁₂alkenyls, C₆to C₁₂aryls, C₇to C₂₀alkylaryls, substituted C₁to C₁₂alkyls, substituted C₆to C₁₂aryls, substituted C₇to C₂₀alkylaryls and C₁to C₁₂heteroatom-containing alkyls, C₁to C₁₂heteroatom-containing aryls and C₁to C₁₂heteroatom-containing alkylaryls in yet a more particular embodiment; chloride, fluoride, C₁to C₆alkyls, C₂to C₆alkenyls, C₇to C₁₈alkylaryls, halogenated C₁to C₆alkyls, halogenated C₂to C₆alkenyls, and halogenated C₇to C₁₈alkylaryls in yet a more particular embodiment; fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyls (mono-, di- and trifluoromethyls) and fluorophenyls (mono-, di-, tri-, tetra- and pentafluorophenyls) in yet a more particular embodiment; and fluoride in yet a more particular embodiment.

Non-limiting examples of other X groups include alkyls, amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having from 1 to 20 carbon atoms; fluorinated hydrocarbon radicals (e.g., —C₆F₅(pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF₃C(O)O⁻), hydrides and halogen ions and combinations thereof. Other examples of X ligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like. In one exemplary embodiment, two or more X's form a part of a fused ring or ring system.

In another exemplary embodiment, the supported bimetallic catalyst includes a metallocene catalyst component such as those of formula (I) where Cp^Aand Cp^Bare bridged to each other by at least one bridging group, (A), such that the structure is represented by formula (II):
Cp^A(A)Cp^BMX_n (II)

These bridged compounds represented by formula (II) are known as “bridged metallocenes.” The elements Cp^A, Cp^B, M, X and n in structure (II) are as defined above for formula (I), each Cp ligand is chemically bonded to M, and (A) is chemically bonded to each Cp ligand. Non-limiting examples of bridging group (A) include divalent hydrocarbon groups containing at least one Group 13 to 16 atom, such as, but not limited to, at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom, and combinations thereof, wherein the heteroatom may also be C₁to C₁₂alkyl- or aryl-substituted to satisfy neutral valency. The bridging group (A) may also contain substituent groups R as defined above (for formula (I)), including halogen radicals and iron. More particular non-limiting examples of bridging group (A) are represented by C₁to C₆alkylenes, substituted C₁to C₆alkylenes, oxygen, sulfur, R′₂C—, R′₂Si—, —Si(R′)₂Si(R′₂)—, R′₂Ge—, R′P— (wherein “—” represents two chemical bonds), where R′ is independently selected from the group consisting of hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted Group 15 atoms, substituted Group 16 atoms, and halogen radical; and wherein two or more R′ may be joined to form a ring or ring system. In one exemplary embodiment, the bridged metallocene catalyst component of formula (II) has two or more bridging groups (A).

Other non-limiting examples of bridging group (A) include methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1,2-dimethylethylene, 1,2-diphenylethylene, 1,1,2,2-tetramethylethylene, dimethylsilyl, diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl, di(n-propyl)silyl, di(i-propyl)silyl, di(n-hexyl)silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di(t-butylphenyl)silyl, di(p-tolyl)silyl and the corresponding moieties wherein the Si atom is replaced by a Ge or a C atom; dimethylsilyl, diethylsilyl, dimethylgermyl and diethylgermyl.

In another exemplary embodiment, bridging group (A) may also be cyclic, comprising, for example, 4 to 10 ring members; in a more particular exemplary embodiment, bridging group (A) may comprise 5 to 7 ring members. The ring members may be selected from the elements mentioned above, and, in a particular exemplary embodiment, are selected from one or more of B, C, Si, Ge, N and O. Non-limiting examples of ring structures which may be present as, or as part of, the bridging moiety are cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene and the corresponding rings where one or two carbon atoms are replaced by at least one of Si, Ge, N and O, in a particular exemplary embodiment, Si and Ge. The bonding arrangement between the ring and the Cp groups may be either cis-, trans-, or a combination.

The cyclic bridging groups (A) may be saturated or unsaturated and/or carry one or more substituents and/or be fused to one or more other ring structures. If present, the one or more substituents are, in one exemplary embodiment, selected from the group consisting of hydrocarbyl (e.g., alkyl such as methyl) and halogen (e.g., F, Cl). The one or more Cp groups to which the above cyclic bridging moieties may optionally be fused may be saturated or unsaturated, and are selected from the group consisting of those having 4 to 10 ring members, more particularly 5, 6 or 7 ring members (selected from the group consisting of C, N, O and S in a particular embodiment) such as, for example, cyclopentyl, cyclohexyl and phenyl. Moreover, these ring structures may themselves be fused such as, for example, in the case of a naphthyl group. Moreover, these (optionally fused) ring structures may carry one or more substituents. Illustrative, non-limiting examples of these substituents are hydrocarbyl (particularly alkyl) groups and halogen atoms.

The ligands Cp^Aand Cp^Bof formulae (I) and (II) are different from each other in one examplary embodiment, and the same in another exemplary embodiment.

In yet another exemplary embodiment, the supported bimetallic catalyst includes bridged mono-ligand metallocene compounds (e.g., mono cyclopentadienyl catalyst components). In this embodiment, the metallocene catalyst component is a bridged “half-sandwich” metallocene represented by the formula (III):
Cp^A(A)QMX_r (III)
wherein Cp^Ais defined above and is bound to M;

- (A) is a bridging group bonded to Q and Cp^A;
- an atom from the Q group is bonded to M; and
- r is an integer 0, 1 or 2.
  In formula (III) above, Cp^A, (A) and Q may form a fused ring system. The X groups of formula (III) are as defined above in formula (I) and (II). In one exemplary embodiment, Cp^Ais selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted versions thereof, and combinations thereof.

In formula (III), Q is a heteroatom-containing ligand in which the bonding atom (the atom that is bonded with the metal M) is, in one exemplary embodiment, selected from the group consisting of Group 15 atoms and Group 16 atoms. In yet a more particular embodiment, the bonding atom is selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur atom. In still a more particular embodiment, the bonding atom is selected from the group consisting of nitrogen and oxygen. Non-limiting examples of Q groups include alkylamines, arylamines, mercapto compounds, ethoxy compounds, carboxylates (e.g., pivalate), carbamates, azenyl, azulene, pentalene, phosphoyl, phosphinimine, pyrrolyl, pyrozolyl, carbazolyl, borabenzene other compounds having Group 15 and Group 16 atoms capable of bonding with M.

In yet another exemplary embodiment, the supported bimetallic catalyst includes a component that is an unbridged “half sandwich” metallocene represented by the formula (IVa):
Cp^AMQ_qX_w (IVa)
wherein Cp^Ais defined as for the Cp groups in (I) and is a ligand that is bonded to M;

- each Q is independently bonded to M;
- X is a leaving group as described above in (I);
- w ranges from 0 to 3, and is 0 or 3 in one exemplary embodiment; and
- q ranges from 0 to 3, and is 0 or 3 in one exemplary embodiment.
  In one exemplary embodiment, Cp^Ais selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted version thereof, and combinations thereof.

In formula (IVa), Q is selected from the group consisting of ROO⁻, RO—, R(O)—, —NR—, —CR₂—, —S—, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, —H, and substituted and unsubstituted aryl groups, R is selected from the group consisting of C₁to C₆alkyls, C₆to C₁₂aryls, C₁to C₆alkylamines, C₆to C₁₂alkylarylamines, C₁to C₆alkoxys, C₆to C₁₂aryloxys, and the like. Non-limiting examples of Q include C₁to C₁₂carbamates, C₁to C₁₂carboxylates (e.g., pivalate), C₂to C₂₀allyls, and C₂to C₂₀heteroallyl moieties.

Described another way, the “half sandwich” metallocenes above can be described as in formula (IVb), such as described in, for example, U.S. Pat. No. 6,069,213:
Cp^AM(W₂GZ)X_yor
T(Cp^AM(W₂GZ)X_y) _m (IVb)
wherein M, Cp^A, and X are as defined above;

W₂GZ forms a polydentate ligand unit (e.g., pivalate), wherein at least one of the W groups form a bond with M, and is defined such that each W is independently selected from the group consisting of —O—, —NR—, —CR₂— and —S—; G is either carbon or silicon; and Z is selected from the group consisting of R, —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, and hydride, providing that when W is —NR—, then Z is selected from the group consisting of —OR, —NR₂, —SR, —SiR₃, —PR₂; and provided that neutral valency for W is satisfied by Z; and wherein each R is independently selected from the group consisting of C₁to C₁₀heteroatom containing groups, C₁to C₁₀alkyls, C₆to C₁₂aryls, C₆to C₁₂alkylaryls, C₁to C₁₀alkoxys, and C₆to C₁₂aryloxys;
y is 1 or 2 in a particular embodiment;
T is a bridging group selected from the group consisting of C₁to C₁₀alkylenes, C₆to C₁₂arylenes and C₁to C₁₀heteroatom containing groups, and C₆to C₁₂heterocyclic groups; wherein each T group bridges adjacent “Cp^AM(W₂GZ)X_y” groups, and is chemically bonded to the Cp^Agroups; and
m is an integer from 1 to 7. In an exemplary embodiment, m is an integer from 2 to 6.

In another aspect of the invention, the supported bimetallic catalyst includes a ene catalyst component that can be described more particularly in structures (Va), (Vb), (Vc) and (Vd):

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wherein in structures (Va) to (Vd) M is selected from the group consisting of Group 3 to Group 12 atoms, and selected from the group consisting of Group 3 to Group 10 atoms in a more particular embodiment, and selected from the group consisting of Group 3 to Group 6 atoms in yet a more particular embodiment, and selected from the group consisting of Group 4 atoms in yet a more particular embodiment, and selected from the group consisting of Zr and Hf in yet a more particular embodiment; and is Zr in yet a more particular embodiment;
wherein Q in (Va-i) and (Va-ii) is selected from the group consisting of halogen ions, alkyls, alkylenes, aryls, arylenes, alkoxys, aryloxys, amines, alkylamines, phosphines, alkylphosphines, substituted alkyls, substituted aryls, substituted alkoxys, substituted aryloxys, substituted amines, substituted alkylamines, substituted phosphines, substituted alkylphosphines, carbamates, heteroallyls, carboxylates (non-limiting examples of suitable carbamates and carboxylates include triethylacetate, trimethylacetate, methylacetate, p-toluate, benzoate, diethylcarbamate, and dimethylcarbamate), fluorinated alkyls, fluorinated aryls, and fluorinated alkylcarboxylates;
q is an integer ranging from 1 to 3;
wherein each R* is independently selected from the group consisting of hydrocarbyls and heteroatom-containing hydrocarbyls in one exemplary embodiment; and selected from the group consisting of alkylenes, substituted alkylenes and heteroatom-containing hydrocarbyls in another exemplary embodiment; and independently selected from the group consisting of C₁to C₁₂alkylenes, C₁to C₁₂substituted alkylenes, and C₁to C₁₂heteroatom-containing hydrocarbons in a more particular embodiment; and independently selected from the group consisting of C₁to C₄alkylenes in yet a more particular embodiment; and wherein both R* groups are identical in another exemplary embodiment in structures (Vb-d);
A is as described above for (A) in structure (II), and more particularly, selected from the group consisting of —O—, —S—, —SO₂—, —NR—, —SiR₂, —GeR₂, —SnR₂, —R₂SiSiR₂—, RP—, C₁to C₁₂alkylenes, substituted C₁to C₁₂alkylenes, divalent C₄to C₁₂cyclic hydrocarbons and substituted and unsubstituted aryl groups in one exemplary embodiment; and selected from the group consisting of C₅to C₈cyclic hydrocarbons, —CH₂CH₂—, —CR₂and —SiR₂in a more particular embodiment; wherein and R is selected from the group consisting of alkyls, cycloalkyls, aryls, alkoxys, fluoroalkyls and heteroatom-containing hydrocarbons in one exemplary embodiment; and R is selected from the group consisting of C₁to C₆alkyls, substituted phenyls, phenyl, and C₁to C₆alkoxys in a more particular embodiment; and R is selected from the group consisting of methoxy, methyl, phenoxy, and phenyl in yet a more particular embodiment;
wherein A may be absent in yet another exemplary embodiment, in which case each R* is defined as for R¹-R¹²;
each X is as described above in (I);
n is an integer from 0 to 4, and from 1 to 3 in another exemplary embodiment, and 1 or 2 in yet another exemplary embodiment; and
R¹through R¹²are independently selected from the group consisting of hydrogen radical, halogen radicals, C₁to C₁₂alkyls, C₂to C₁₂alkenyls, C₆to C₁₂aryls, C₇to C₂₀alkylaryls, C₁to C₁₂alkoxys, C_lto C₁₂fluoroalkyls, C₆to C₁₂fluoroaryls, and C₁to C₁₂heteroatom-containing hydrocarbons and substituted derivatives thereof, in one exemplary embodiment; independently selected from the group consisting of hydrogen radical, fluorine radical, chlorine radical, bromine radical, C₁to C₆alkyls, C₂to C₆alkenyls, C₇to C₁₈alkylaryls, C₁to C₆fluoroalkyls, C₂to C₆fluoroalkenyls, C₇to C₁₈fluoroalkylaryls in a more particular embodiment; and hydrogen radical, fluorine radical, chlorine radical, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, hexyl, phenyl, 2,6-di-methylphenyl, and 4-tertiarybutylphenyl groups in yet a more particular embodiment; wherein adjacent R groups may form a ring, either saturated, partially saturated, or completely saturated.

The structure of the metallocene catalyst component represented by (Va) may take on many forms, such as those disclosed in, for example, U.S. Pat. No. 5,026,798, U.S. Pat. No. 5,703,187, and U.S. Pat. No. 5,747,406, including a dimer or oligomeric structure, such as disclosed in, for example, U.S. Pat. No. 5,026,798 and U.S. Pat. No. 6,069,213.

In a particular embodiment of the metallocene represented in (Vd), R¹and R²form a conjugated 6-membered carbon ring system that may or may not be substituted.

Non-limiting examples of metallocene catalyst components consistent with the description herein include:

cyclopentadienylzirconium X_n,
indenylzirconium X_n,
(1-methylindenyl)zirconium X_n,
(2-methylindenyl)zirconium X_n,
(1-propylindenyl)zirconium X_n,
(2-propylindenyl)zirconium X_n,
(1-butylindenyl)zirconium X_n,
(2-butylindenyl)zirconium X_n,
(methylcyclopentadienyl)zirconium X_n,
tetrahydroindenylzirconium X_n,
(pentamethylcyclopentadienyl)zirconium X_n,
cyclopentadienylzirconium X_n,
pentamethylcyclopentadienyltitanium X_n,
tetramethylcyclopentyltitanium X_n,
1,2,4-trimethylcyclopentadienylzirconium X_n,
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl )(cyclopentadienyl)zirconium X_n,
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl )(1,2,3-trimethyl-cyclopentadienyl)zirconium X_n,
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl )(1,2-dimethyl-cyclopentadienyl)zirconium X_n,
dimethylsilyl(1,2,3,4-tetramethyl-cyclopentadieny l)(2-methylcyclopentadienyl)zirconium X_n,
dimethylsilyl(cyclopentadienyl)(indenyl)zirconium X_n,
dimethylsilyl(2-methylindenyl)(fluorenyl)zirconiu m X_n,
diphenylsilyl(1,2,3,4-tetramethyl-cyclopentadieny l)(3-propylcyclopentadienyl)zirconium X_n,
dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl ) (3-t-butylcyclopentadienyl)zirconium X_n,
dimethylgermyl(1,2-dimethylcyclopentadienyl)(3-is opropylcyclopentadienyl)zirconium X_n,
dimethylsilyl(1,2,3,4-tetramethyl-cyclopentadieny l)(3-methylcyclopentadienyl)zirconium X_n,
diphenylmethylidene(cyclopentadienyl)(9-fluorenyl )zirconium X_n,
diphenylmethylidene(cyclopentadienyl)(indenyl)zir conium X_n,
iso-propylidenebis(cyclopentadienyl)zirconium X_n,
iso-propylidene(cyclopentadienyl)(9-fluorenyl)zir conium X_n,
iso-propylidene(3-methylcyclopentadienyl)(9-fluor enyl)zirconium X_n,
ethylenebis(9-fluorenyl)zirconium X_n,
meso-ethylenebis(1-indenyl)zirconium X_n,
ethylenebis(1-indenyl)zirconium X_n,
ethylenebis(2-methyl-1-indenyl)zirconium X_n,
ethylenebis(2-methyl-4,5,6,7-tetrahydro-1-indenyl )zirconium X_n,
ethylenebis(2-propyl-4,5,6,7-tetrahydro-1-indenyl )zirconium X_n,
ethylenebis(2-isopropyl-4,5,6,7-tetrahydro-1-inde nyl)zirconium X_n,
ethylenebis(2-butyl-4,5,6,7-tetrahydro-1-indenyl) zirconium X_n,
ethylenebis(2-isobutyl-4,5,6,7-tetrahydro-1-inden yl)zirconium X_n,
dimethylsilyl(4,5,6,7-tetrahydro-1-indenyl)zircon ium X_n,
diphenyl(4,5,6,7-tetrahydro-1-indenyl)zirconium X_n,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconiu m X_n,
dimethylsilylbis(cyclopentadienyl)zirconium X_n,
dimethylsilylbis(9-fluorenyl)zirconium X_n,
dimethylsilylbis(1-indenyl)zirconium X_n,
dimethylsilylbis(2-methylindenyl)zirconium X_n,
dimethylsilylbis(2-propylindenyl)zirconium X_n,
dimethylsilylbis(2-butylindenyl)zirconium X_n,
diphenylsilylbis(2-methylindenyl)zirconium X_n,
diphenylsilylbis(2-propylindenyl)zirconium X_n,
diphenylsilylbis(2-butylindenyl)zirconium X_n,
dimethylgermylbis(2-methylindenyl)zirconium X_n,
dimethylsilylbis(tetrahydroindenyl)zirconium X_n,
dimethylsilylbis(tetramethylcyclopentadienyl)zirc onium X_n,
dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirco nium X_n,
diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirco nium X_n,
diphenylsilylbis(indenyl)zirconium X_n,
cyclotrimethylenesilyl(tetramethylcyclopentadieny l)(cyclopentadienyl)zirconium X_n,
cyclotetramethylenesilyl(tetramethylcyclopentadie nyl)(cyclopentadienyl)zirconium X_n,
cyclotrimethylenesilyl(tetramethylcyclopentadieny l)(2-methylindenyl)zirconium X_n,
cyclotrimethylenesilyl(tetramethylcyclopentadieny l)(3-methylcyclopentadienyl)zirconium X_n,
cyclotrimethylenesilylbis(2-methylindenyl)zirconi um X_n,
cyclotrimethylenesilyl(tetramethylcyclopentadieny l)(2,3,5-trimethylcyclopentadienyl)zirconium X_n,
cyclotrimethylenesilylbis(tetramethylcyclopentadi enyl)zirconium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(N-tert -butylamido)titanium X_n,
bis(cyclopentadienyl)chromium X_n,
bis(cyclopentadienyl)zirconium X_n,
bis(n-butylcyclopentadienyl)zirconium X_n,
bis(n-dodecyclcyclopentadienyl)zirconium X_n,
bis(ethylcyclopentadienyl)zirconium X_n,
bis(iso-butylcyclopentadienyl)zirconium X_n,
bis(iso-propylcyclopentadienyl)zirconium X_n,
bis(methylcyclopentadienyl)zirconium X_n,
bis(n-oxtylcyclopentadienyl)zirconium X_n,
bis(n-pentylcyclopentadienyl)zirconium X_n,
bis(n-propylcyclopentadienyl)zirconium X_n,
bis(trimethylsilylcyclopentadienyl)zirconium X_n,
bis(1,3-bis(trimethylsilyl)cyclopentadienyl)zirco nium X_n,
bis(1-ethyl-2-methylcyclopentadienyl)zirconium X_n,
bis(1-ethyl-3-methylcyclopentadienyl)zirconium X_n,
bis(pentamethylcyclopentadienyl)zirconium X_n,
bis(pentamethylcyclopentadienyl)zirconium X_n,
bis(1-propyl-3-methylcyclopentadienyl)zirconium X_n,
bis(1-n-butyl-3-methylcyclopentadienyl)zirconium X_n,
bis(1-isobutyl-3-methylcyclopentadienyl)zirconium X_n,
bis(1-propyl-3-butylcyclopentadienyl)zirconium X_n,
bis(1,3-n-butylcyclopentadienyl)zirconium X_n,
bis(4,7-dimethylindenyl)zirconium X_n,
bis(indenyl)zirconium X_n,
bis(2-methylindenyl)zirconium X_n,
cyclopentadienylindenylzirconium X_n,
(tetramethylcyclopentadienyl)(n-propylcyclopentad ienyl)zirconium X_n,
(pentamethylcyclopentadienyl)(n-propylcyclopentad ienyl)zirconium X_n,
bis(n-propylcyclopentadienyl)hafnium X_n,
bis(n-butylcyclopentadienyl)hafnium X_n,
bis(n-pentylcyclopentadienyl)hafnium X_n,
(n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafnium X_n,
bis[(2-trimethylsilylethyl)cyclopentadienyl]hafni um X_n,
bis(trimethylsilyl cyclopentadienyl)hafnium X_n,
bis(2-n-propylindenyl)hafnium X_n,
bis(2-n-butylindenyl)hafnium X_n,
dimethylsilylbis(n-propylcyclopentadienyl)hafnium X_n,
dimethylsilylbis(n-butylcyclopentadienyl)hafnium X_n,
bis(9-n-propylfluorenyl)hafnium X_n,
bis(9-n-butylfluorenyl)hafnium X_n,
(9-n-propylfluorenyl)(2-n-propylindenyl)hafnium X_n,
bis(1-n-propyl-2-methylcyclopentadienyl)hafnium X_n,
(n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcy clopentadienyl)hafnium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(cyclop ropylamido)titanium X_n,
dimethylsilyl(tetramethyleyclopentadienyl)(cyclob utylamido)titanium X_n,
dimethylsilyl(tetramethyleyclopentadienyl)(cyclop entylamido)titanium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(cycloh exylamido)titanium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(cycloh eptylamido)titanium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(cycloo ctylamido)titanium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(cyclon onylamido)titanium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(cyclod ecylamido)titanium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(cyclou ndecylamido)titanium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(cyclod odecylamido)titanium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(sec-bu tylamido)titanium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(n-octy lamido)titanium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(n-decy lamido)titanium X_n,
dimethylsilyl(tetramethylcyclopentadienyl)(n-octa decylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(cy clopropylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(cy clobutylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(cy clopentylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(cy clohexylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(cy cloheptylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(cy clooctylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(cy clononylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(cy clodecylamido)titanium, X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(cy cloundecylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(cy clododecylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(se c-butylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(n- octylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(n- decylamido)titanium X_n,
methylphenylsilyl(tetramethylcyclopentadienyl)(n- octadecylamido)titanium X_n,
diphenylsilyl(tetramethylcyclopentadienyl)(cyclop ropylamido)titanium X_n,
diphenylsilyl(tetramethylcyclopentadienyl)(cyclob utylamido)titanium X_n,
diphenylsilyl(tetramethylcyclopentadienyl)(cyclop entylamido)titanium X_n,
diphenylsilyl(tetramethylcyclopentadienyl)(cycloh exylamido)titanium X_n,
diphenylsilyl(tetramethylcyclopentadienyl)(cycloh eptylamido)titanium X_n,
diphenylsilyl(tetramethylcyclopentadienyl)(cycloo ctylamido)titanium X_n,
diphenylsilyl(tetramethylcyclopentadienyl)(cyclon onylamido)titanium X_n,
diphenylsilyl(tetramethylcyclopentadienyl)(cyclod ecylamido)titanium X_n,
diphenylsilyl(tetramethylcyclopentadienyl)(cyclou ndecylamido)titanium X_n,
diphenylsilyl(tetramethylcyclopentadienyl)(cyclod odecylamido)titanium X_n,
diphenylsilyl(tetramethylcyclopentadienyl)(sec-bu tylamido)titanium X_n,
diphenylsilyl(tetramethyleyclopentadienyl)(n-octy lamido)titanium X_n,
diphenylsilyl(tetramethyleyclopentadienyl)(n-decy lamido)titanium X_n,
diphenylsilyl(tetramethylcyclopentadienyl)(n-octa decylamido)titanium X_n, and derivatives thereof,
wherein the value of n is 1, 2 or 3. The phrase “derivatives thereof” will be understood to mean any substitution or ring formation as described above for structures (Va-d) in one exemplary embodiment; and in particular, replacement of the metal “M” (Cr, Zr, Ti or Hf) with an atom selected from the group consisting of Cr, Zr, Hf and Ti; and replacement of the “X” group with any of C₁to C₅alkyls, C₆aryls, C₆to C₁₀alkylaryls, fluorine, chlorine, or bromine.

It is contemplated that the metallocene catalysts components described above include their structural or optical or enantiomeric isomers (racemic mixture), and, in one exemplary embodiment, may be a pure enantiomer.

As used herein, a single, bridged, asymmetrically substituted metallocene catalyst component having a racemic and/or meso isomer does not, itself, constitute at least two different bridged, metallocene catalyst components.

The “metallocene catalyst component” useful in the present invention may comprise any combination of any “embodiment” described herein.

When combined to form the bimetallic catalyst component, the molar ratio of metal from the first catalyst component to the second catalyst component (e.g., molar ratio of Ti:Zr) is a value of from 0.1:1 to 20:1 in one exemplary embodiment; and from 1:1 to 18:1 in another exemplary embodiment, and from 2:1 to 15:1 in yet another exemplary embodiment, and from 3:1 to 12:1 in yet another exemplary embodiment; and from 4:1 to 10:1 in yet another exemplary embodiment, and from 4:1 to 8:1 in yet another exemplary embodiment; wherein a desirable molar ratio of first catalyst component metal:second catalyst component metal is any combination of any upper limit with any lower limit described herein.

MAO-Activatable Compound

A “supported, treated catalyst system” comprises a bimetallic catalyst system that has been contacted with at least one compound that can be activated by methylalumoxane (“MAO-activatable compound”). Because the MAO-activatable compounds used with the present invention generally include transition metals, the supported, treated catalyst systems of the present invention generally have greater concentrations of transition metals (which can be activated by MAO) than do bimetallic catalyst systems. For example, in one embodiment, the supported, treated catalyst systems of the present invention have a transition metal concentration that is up to 25% greater than that of a typical bimetallic catalyst system; in another exemplary embodiment, the supported, treated catalyst systems of the present invention have a transition metal concentration that is more than 25% greater than that of a typical bimetallic catalyst system. Accordingly, the supported, treated catalyst systems of the present invention generally demonstrate more efficient use of MAO when they are used in polymerization processes than do typical bimetallic catalyst systems.

In an exemplary embodiment of the present invention, the at least one MAO-activatable compound is a metallocene catalyst compound, non-limiting examples of which have been previously described. In another exemplary embodiment, the at least one MAO-activatable compound is a Group-15-component-containing compound; a phenoxide catalyst compound; an additionally-discovered catalyst compound; or a conventional transition metal catalyst compound.

Group-15-Component-Containing Catalyst Compound

The at least one MAO-activatable compound may include one or more Group-15-component-containing catalyst compounds. The Group-15-component-containing compound generally includes a Group 3 to 14 metal atom, preferably a Group 3 to 7, more preferably a Group 4 to 6, and even more preferably a Group 4 metal atom, bound to at least one leaving group and also bound to at least two Group 15 atoms, at least one of which is also bound to a Group 15 or 16 atom through another group.

In one embodiment, at least one of the Group 15 atoms is also bound to a Group 15 or 16 atom through another group which may be a C₁to C₂₀hydrocarbon group, a heteroatom containing group, silicon, germanium, tin, lead, or phosphorus, wherein the Group 15 or 16 atom may also be bound to nothing or a hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group, and wherein each of the two Group 15 atoms are also bound to a cyclic group and may optionally be bound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a heteroatom containing group.

In another embodiment, the Group-15-component-containing compound of the present invention may be represented by the formulae:

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wherein M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal, preferably a Group 4, 5, or 6 metal, and more preferably a Group 4 metal, and most preferably zirconium, titanium or hafnium,
- each X is independently a leaving group, preferably, an anionic leaving group, and more preferably hydrogen, a hydrocarbyl group, a heteroatom or a halogen, and most preferably an alkyl;
- y is 0 or 1 (when y is 0, group L′ is absent),
- n is the oxidation state of M, preferably +3, +4, or +5, and more preferably +4,
- m is the formal charge of the YZL or the YZL′ ligand, preferably 0, −1, −2 or −3, and more preferably −2,
- L is a Group 15 or 16 element, preferably nitrogen,
- L′ is a Group 15 or 16 element or Group 14 containing group, preferably carbon, silicon or germanium,
- Y is a Group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen,
- Z is a Group 15 element, preferably nitrogen or phosphorus, and more preferably nitrogen,
- R¹and R²are independently a C₁to C₂₀hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, halogen or phosphorus, preferably a C₂to C₂₀alkyl, aryl or aralkyl group, more preferably a linear, branched or cyclic C₂to C₂₀alkyl group, most preferably a C₂to C₆hydrocarbon group. R¹and R²may also be interconnected to each other.
- R³is absent or a hydrocarbon group, hydrogen, a halogen, a heteroatom containing group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably R³is absent, hydrogen or an alkyl group, and most preferably hydrogen,
- R⁴and R⁵are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or multiple ring system, preferably having up to 20 carbon atoms, more preferably between 3 and 10 carbon atoms, and even more preferably a C₁to C₂₀hydrocarbon group, a C₁to C₂₀aryl group or a C to C₂₀aralkyl group, or a heteroatom containing group, for example PR³, where R is an alkyl group,
- R¹and R²may be interconnected to each other, and/or R⁴and R⁵may be interconnected to each other,
- R⁶and R⁷are independently absent, or hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably absent, and
- R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.

The term “formal charge of the YZL or YZL′ ligand,” refers to the charge of the entire ligand absent the metal and the leaving groups X. The term “R¹and R²may also be interconnected” means that R¹and R²may be directly bound to each other or may be bound to each other through other groups. The term “R⁴and R⁵may also be interconnected” means that R⁴and R⁵may be directly bound to each other or may be bound to each other through other groups.

An alkyl group may be a linear, branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or combination thereof. An aralkyl group is defined to be a substituted aryl group.

In an exemplary embodiment, R⁴and R⁵are independently a group represented by the following formula:

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wherein:

R¹to R¹²are each independently hydrogen, a C₁to C₄₀alkyl group, a halide, a heteroatom, a heteroatom containing group containing up to 40 carbon atoms, preferably a C₁to C₂₀linear or branched alkyl group, preferably a methyl, ethyl, propyl or butyl group, any two R groups may form a cyclic group and/or a heterocyclic group. The cyclic groups may be aromatic. In a preferred embodiment R⁹, R¹⁰and R¹²are independently a methyl, ethyl, propyl or butyl group (including all isomers), in a preferred embodiment R⁹, R¹⁰and R¹²are methyl groups, and R⁸and R¹¹are hydrogen.

In a particular exemplary embodiment, R⁴and R⁵are both a group represented by the following formula:

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In this embodiment, M is a Group 4 metal, preferably zirconium, titanium or hafnium, and even more preferably zirconium; each of L, Y, and Z is nitrogen; each of R¹and R²is —CH2 —CH2—; R³is hydrogen; and R⁶and R⁷are absent.

In a particular exemplary embodiment, the Group-15-component-containing compound is represented by Compound 1 below:

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wherein “Ph” represents a phenyl group.

In exemplary embodiments of the present invention where the at least one MAO-activatable compound includes a Group-15-component-containing compound, the Group-15-component-containing compound may be prepared by methods known in the art, such as those disclosed in EP 0 893 454 A1, U.S. Pat. No. 5,889,128 and the references cited in U.S. Pat. No. 5,889,128. U.S. patent application Ser. No. 09/312,878, filed May 17, 1999, now U.S. Pat. No. 6,271,325, discloses a gas or slurry phase polymerization process using a supported bisamide catalyst.

A preferred direct synthesis of these compounds comprises reacting the neutral ligand, (see for example YZL or YZL′ of formula VI or VII) with MⁿX_n(M is a Group 3 to 14 metal, n is the oxidation state of M, each X is an anionic group, such as halide), in a non-coordinating or weakly coordinating solvent, such as ether, toluene, xylene, benzene, methylene chloride, and/or hexane or other solvent having a boiling point above 60° C., at about 20 to about 150° C. (preferably 20 to 100° C.), preferably for 24 hours or more, then treating the mixture with an excess (such as four or more equivalents) of an alkylating agent, such as methyl magnesium bromide in ether. The magnesium salts are removed by filtration, and the metal complex isolated by standard techniques.

In one embodiment the Group-15-component-containing compound is prepared by a method comprising reacting a neutral ligand, (see for example YZL or YZL′ of formula VI or VII) with a compound represented by the formula MⁿX_n(where M is a Group 3 to 14 metal, n is the oxidation state of M, each X is an anionic leaving group) in a non-coordinating or weakly coordinating solvent, at about 20° C. or above, preferably at about 20 to about 100° C., then treating the mixture with an excess of an alkylating agent, then recovering the metal complex. In a preferred embodiment the solvent has a boiling point above 60° C., such as toluene, xylene, benzene, and/or hexane. In another embodiment the solvent comprises ether and/or methylene chloride, either being preferable.

Additional information pertaining to Group-15-component-containing compounds may be found in, inter alia, EP 0 893 454 A1, which discloses transition metal amides combined with activators to polymerize olefins.

In one embodiment the Group-15-component-containing compound is allowed to age prior to use in a polymerization. It has been noted on at least one occasion that one such catalyst compound (aged at least 48 hours) performed better than a newly prepared catalyst compound.

Phenoxide Catalyst Compound

The at least one MAO-activatable compound may include one or more phenoxide catalyst compounds represented by the following formulae:

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wherein R¹is hydrogen or a C₄to C₁₀₀group, preferably a tertiary alkyl group, preferably a C₄to C₂₀alkyl group, preferably a C₄to C₂₀tertiary alkyl group, preferably a neutral C₄to C₁₀₀group and may or may not also be bound to M, and at least one of R²to R⁵is a group containing a heteroatom, the rest of R²to R⁵are independently hydrogen or a C₁to C₁₀₀group, preferably a C₄to C₂₀alkyl group (preferably butyl, isobutyl, pentyl hexyl, heptyl, isohexyl, octyl, isooctyl, decyl, nonyl, dodecyl) and any of R²to R⁵also may or may not be bound to M, O is oxygen, M is a group 3 to group 10 transition metal or lanthanide metal, preferably a group 4 metal, preferably Ti, Zr or Hf, n is the valence state of the metal M, preferably 2, 3, 4, or 5, Q is an alkyl, halogen, benzyl, amide, carboxylate, carbamate, thiolate, hydride or alkoxide group, and may be bound to an R group containing a heteroatom, which may be any of R¹to R⁵. A heteroatom containing group may be any heteroatom or a heteroatom bound to carbon silica or another heteroatom. Preferred heteroatoms include boron, aluminum, silicon, nitrogen, phosphorus, arsenic, tin, lead, antimony, oxygen, selenium, tellurium. Particularly preferred heteroatoms include nitrogen, oxygen, phosphorus, and sulfur. Even more particularly preferred heteroatoms include oxygen and nitrogen. The heteroatom itself may be directly bound to the phenoxide ring or it may be bound to another atom or atoms that are bound to the phenoxide ring. The heteroatom containing group may contain one or more of the same or different heteroatoms. Preferred heteroatom groups include imines, amines, oxides, phosphines, ethers, ketenes, oxoazolines heterocyclics, oxazolines, thioethers, and the like. Particularly preferred heteroatom groups include imines. Any two adjacent R groups may form a ring structure, preferably a 5 or 6 membered ring. Likewise, the R groups may form multi-ring structures. In one embodiment any two or more R groups do not form a 5 membered ring.

In an exemplary embodiment, Q is bound to any of R²to R⁵and the R group to which Q is bound is a heteroatom-containing group.

This invention may also be practiced with the catalysts disclosed in EP 0 874 005 A1.

In an exemplary embodiment, the phenoxide catalyst compound includes one or more of:

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium (IV) dibenzyl;
bis(N-ethyl-3,5-di-t-butylsalicylimino)zirconium( IV) dibenzyl;
bis(N-iso-propyl-3,5-di-t-butylsalicylimino)zirco nium(IV) dibenzyl;
bis(N-t-butyl-3,5-di-t-butylsalicylimino)zirconiu m(IV) dibenzyl;
bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium (IV) dibenzyl;
bis(N-hexyl-3,5-di-t-butylsalicylimino)zirconium( IV) dibenzyl;
bis(N-phenyl-3,5-di-t-butylsalicylmino)zirconium( IV) dibenzyl;
bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium (IV) dibenzyl;
bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium (IV) dichloride;
bis(N-benzyl-3,5-di-t-butyl salicylimino)zirconium(IV) dipivalate;
bis(N-benzyl-3,5-di-t-butylsalicylimino)titanium( IV) dipivalate;
bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium (IV) di(bis(dimethylamide));
bis(N-iso-propyl-3,5-di-t-amylsalicylimino)zircon ium(IV) dibenzyl;
bis(N-iso-propyl-3,5-di-t-octylsalicylimino)zirco nium(IV) dibenzyl;
bis(N-iso-propyl-3,5-di-(1′,1′-dimethylbenzyl )salicylimino)zirconium(IV) dibenzyl;
bis(N-iso-propyl-3,5-di-(1′,1′-dimethylbenzyl )salicylimino)titanium(IV) dibenzyl;
bis(N-iso-propyl-3,5-di-(1′,1′-dimethylbenzyl )salicylimino)hafnium(IV) dibenzyl;
bis(N-iso-butyl-3,5-di-(1′,1′-dimethylbenzyl) salicylimino)zirconium(IV) dibenzyl;
bis(N-iso-butyl-3,5-di-(1′,1′-dimethylbenzyl) salicylimino)zirconium(IV) dichloride;
bis(N-hexyl-3,5-di-(1′,1′-dimethylbenzyl)sali cylimino)zirconium(IV) dibenzyl;
bis(N-phenyl-3,5-di-(1′,1′-dimethylbenzyl)sal icylimino)zirconium(IV) dibenzyl;
bis(N-iso-propyl-3,5-di-(1′-methylcyclohexyl)sa licylimino)zirconium(IV) dibenzyl;
bis(N-benzyl-3-t-butylsalicylimino)zirconium(IV) dibenzyl;
bis(N-benzyl-3-triphenylmethylsalicylimino)zircon ium(IV) dibenzyl;
bis(N-iso-propyl-3,5-di-trimethylsilylsalicylimin o)zirconium(IV) dibenzyl;
bis(N-iso-propyl-3-(phenyl)salicylimino)zirconium (IV) dibenzyl;
bis(N-benzyl-3-(2′,6′-di-iso-propylphenyl)sal icylimino)zirconium(IV) dibenzyl;
bis(N-benzyl-3-(2′,6′-di-phenylphenyl)salicyl imino)zirconium(IV) dibenzyl;
bis(N-benzyl-3-t-butyl-5-methoxysalicylimino)zirc onium(IV) dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxi de)zirconium(IV) dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxi de)zirconium(IV) dichloride;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxi de)zirconium(IV) di(bis(dimethylamide));
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-di methylbenzyl)phenoxide)zirconium(IV) dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxi de)titanium(IV)dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-di methylbenzyl)phenoxide)titanium(IV)dibenzyl;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-di methylbenzyl)phenoxide)titanium(IV)dichloride;
bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-di methylbenzyl)phenoxide)hafnium(IV)dibenzyl;
(N-phenyl-3,5-di-(1′,1′-dimethylbenzyl)salicy limino)zirconium(IV)tribenzyl;
(N-(2′,6′-di-iso-propylphenyl)-3,5-di-(1′,1 ′-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;
(N-(2′,6′-di-iso-propylphenyl)-3,5-di-(1′,1 ′-dimethylbenzyl)salicylimino)titanium(IV)tribenzyl; and (N-(2′,6′-di-iso-propylphenyl)-3,5-di-(1′,1′-dimethy lbenzyl)salicylimino)zirconium(IV) trichloride.
Additionally-Discovered Catalyst Compounds

The at least one MAO-activatable compound may include one or more complexes known as transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, such as those described in U.S. patent application Ser. No. 09/103,620, filed Jun. 23, 1998 now U.S. Pat. No. 6,103,657.

In one embodiment, these catalyst compounds are represented by the formula:
((Z)XA_t(YJ))_qMQ_n Formula XII
where M is a metal selected from Group 3 to 13 or lanthanide and actinide series of the Periodic Table of Elements; Q is bonded to M and each Q is a monovalent, bivalent, or trivalent anion; X and Y are bonded to M; one or more of X and Y are heteroatoms, preferably both X and Y are heteroatoms; Y is contained in a heterocyclic ring J, where J comprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbon atoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms, preferably 1 to 50 carbon atoms, preferably Z is a cyclic group containing 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1; when t is 1, A is a bridging group joined to at least one of X, Y or J, preferably X and J; q is 1 or 2; n is an integer from 1 to 4 depending on the oxidation state of M. In one embodiment, where X is oxygen or sulfur then Z is optional. In another embodiment, where X is nitrogen or phosphorous then Z is present. In an embodiment, Z is preferably an aryl group, more preferably a substituted aryl group.

In one exemplary embodiment, the catalyst compounds include complexes of Ni²+ and Pd²⁺ described in the articles Johnson, et al., “New Pd(II)— and Ni(II)— Based Catalysts for Polymerization of Ethylene and a-Olefins,” J. Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson et al., “Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium(II) Catalysts,” J. Am. Chem. Soc., 1996, 118, 267-268, and WO 96/23010 published Aug. 1, 1996, WO 99/02472, U.S. Pat. Nos. 5,852,145, 5,866,663 and 5,880,241. These complexes can be either dialkyl ether adducts, or alkylated reaction products of the described dihalide complexes that can be activated to a cationic state by the activators of this invention described below.

Other catalyst compounds include

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