ZA200501173B - Process for producing fluorinated catalysts - Google Patents

Description

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PROCESS FOR PRODUCING

' FLUORINATED CATALYSTS . FIELD OF INVENTION

[0001] This application relates to a process for forming fluorinated catalyst compounds, and in particular, to producing fluorided metallocene catalyst components and using them as part of a bimodal catalyst composition.

[0002] Bimodal polymers produced using two or more different catalyst types— bimetallic catalysts—are of increasing interest, especially in producing polyethylene and other polyolefins. See, for example, US 5,525,678. However, problems exist in using these bimetallic catalysts, especially in the gas phase. One problem is catalyst activity, which should be as high as possible in order to economize the process, as catalysts costs are significant.

[0003] One method of improving catalyst efficiency in gas phase processes is to improve upon the catalyst used in the process. A promising class of single-site catalysts for commercial use includes those wherein the metal center has at least one extractable fluorine (or fluorine “leaving group”). Disclosures of such catalysts include US 20020032287; US 6,303,718; US 6,291,615; US 4,874,880; US 3,896; 179; WO 97/07141; DE 43 32 009 Al; EP-

A2 0 200 351; EP-Al 0 705 $49; E.F. Murphy, et al., Synthesis and spectroscopic characterization of a series of substituted cyclopentadienyl Group 4 fluorides; crystal structure of the acetylacetonato complex [(acac),(1’-CsMes)Zr(u-F)SnMe;Cl], DALTON, 1983 (1996); A.

Herzog, et al, Reactions of (17-CsMes)ZrFs, (17-CsMeEt)ZrFs, (1°-CsM4s),ZrFs, (17- CsMes)HfF;, and (7 -CsMes)TaFy with AlMes, Structure of the First Hafnium-Aluminum-

Carbon Cluster, 15 ORGANOMETALLICS 909-917 (1996); F. Garbassi, et al., JOURNAL OF

MOLECULAR CATALYSIS A: CHEMICAL 101 199-209 (1995); and W. Kaminsky, et al.,

Fluorinated Half-Sandwich Complexes as Catalysts in Syndiospecific Styrene Polymerization, 30(25) MACROMOLECULES 7647-7650 (1997). Use of such single site catalyst components in a olefin polymerization system is desirable, especially in gas-phase polyethylene polymerization.

However, it is often not commercially practical to produce such fluorided metallocene catalysts.

[0004] Methods of fluoriding metallocene catalyst components are disclosed by Z. Xie et al, Synthesis, Molecular Structure, and Reactivity of Organolanthanide Fluoride ‘

Complexes, [{(Me;Si),CsHs}:Ln(u-F)]; (Ln = La, Nd, Sm, Gd) and [(CsHs),Ln(u-F)(THF)], (Ln = Y, Yb), 17 ORGANOMETALLICS 3937-3944 (1998); E.F. Murphy et al. in Organometallic

Fluorides: Compounds Containing Carbon—>Metal—Fluorine Fragments of d-Block Metals, 97 CHEM. REV. 3425-3468 (1997); W.W. Lukens, Jr. et al. in 4 w-Donor Spectrochemical

Series for X in (MesCs),TiX, and p-Agostic Interactions in X = Et and N(Me)Ph, 118 J. AM.

CHEM. Soc. 1729-1728 (1996); and P.M. Druce et al. in Metallocene Halides: - Part I.-

Synthesis, Spectra, and Redistribution Equilibria of Di-n-cyclopentadienyl-Ti(IV), -Zr(IV), and -Hf(IV), 14 J. CHEM. Soc. 2106-2110 (1969). However, these methods fall short of a desirable, cost effect commercial method of making fluorided metallocene catalyst components. It would be desirable to improve the method of producing fluorided metallocenes, as well as its us in bimodal polymerization processes, especially for bimodal gas phase polymerization processes. The present invention is directed towards solving this and other problems.

SUMMARY

[0005] This invention relates to a process for producing fluorided metallocene compounds, a catalyst composition comprising such compounds, and a method of polymerizing olefins using such compounds.

[0006] At least one specific embodiment of the invention includes contacting a metallocene catalyst component, a chlorinated metallocene catalyst compound in a particular embodiment, with a fluoriding agent for a time sufficient to form a fluorinated metallocene catalyst compound. In one or more specific embodiments, the fluoriding agent is or includes a fluorinated inorganic salt. In one or more specific embodiments, the fluoriding agent is in the form of, or part of, a mixture, for example, an aqueous solution. : [0007} Another specific embodiment of the invention is directed to a process of producing a fluorinated catalyst compound, which includes: contacting a metallocene compound having the general formula (CpRp)mMX)3 with a mixture comprising a fluorinated inorganic salt to form a fluorinated metallocene having the formula (CpRp)mMXoF: (Which can o : a include, for example, a partially fluorinated metallocene) wherein Cp is a cyclopentadienyl ring ‘ or derivative thereof, R is a hydrocarbyl group, methyl group or hydrocarboxyl group, M is a

Group 4, 5, or 6 transition metal, X is an anionic ligand such as a halogen, carboxylate, acetylacetonate, alkoxide, hydroxide, or oxide, m=1t03,p=0t0 10,n=0to 3,andr=1to 3.

[0008] Preferably, in any one of the processes identified above or described herein, the ~... fluoriding agent is a mixture, for-example; a-mixture-that comprises water and fluorinated - inorganic salt. Alternatively, the mixture may comprise an organic solvent and the fluorinated inorganic salt. In certain embodiments, the fluoriding agent may be considered the inorganic fluoride salt itself. Various specific embodiments demonstrate unusually high yields in the presence of water. Surprisingly, for example, contacting the chlorinated metallocene described herein with the mixture results in a product yield of 50% or more. More particularly, contacting the chlorinated metallocene with the salt mixture results in a product yield of §0% or more. Even more particularly, contacting the chlorinated metallocene with the salt mixture results in a product yield of 90% or more.

[0009] In a specific embodiment, M is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and combinations thereof. In a more particular embodiment, M is zirconium or hafnium. In another embodiment, the fluorinated metallocene is bridged. In yet another embodiment, p is 0. In a particular embodiment, p is 1 or more (Cp is substituted). In a particular embodiment, p is 2 or more (Cp is disubstituted). )5 DETAILED DESCRIPTION

General Definitions

[0010] As used herein, in reference to Periodic Table "Groups" of Elements, the “new” numbering scheme for the Periodic Table Groups are used as in the CRC HANDBOOK OF

CHEMISTRY AND PHYSICS (David R. Lide ed., CRC Press 81° ed. 2000). Co

[0011] 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, etc., 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, as well as any activator in any combination as described herein.

[0012] 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 comprising at least one Group 3 to Group 12 atom; -and optionally at least one leaving group bound thereto.

[0013] As used herein, the phrase "leaving group" refers to one or more chemical moieties bound to the metal center of the catalyst component that can be abstracted from the catalyst component by an activator, thus producing the species active towards olefin polymerization or oligomerization. The activator is described further below.

[0014] As used herein, the term “fluorided metallocene catalyst component” or “fluorided catalyst component” means a catalyst compound having at least one fluoride or fluorine containing leaving group, preferably a metallocene or metallocene-type catalyst compound having at least one fluoride or fluorine containing leaving group.

[0015] As used herein, a “hydrocarbyl” includes aliphatic, cyclic, olefinic, acetylenic and aromatic radicals (i.e., hydrocarbon radicals) comprising hydrogen and carbon that are deficient by one hydrogen. A “hydrocarbylene” is deficient by two hydrogens.

[0016] As used herein, an “alkyl” includes linear, branched and cyclic paraffin radicals that are deficient by one hydrogen. Thus, for example, a —-CH; group (“methyl”) and a

CH3;CH_— group (“ethyl”) are examples of alkyls. :

[0017] As used herein, an “alkenyl” includes linear, branched and cyclic olefin radicals ' that are deficient by one hydrogen; alkynyl radicals include linear, branched and cyclic acetylene radicals deficient by one hydrogen radical.

®

[0018] As used herein, “aryl” groups includes phenyl, naphthyl, pyridyl and other ’ radicals whose molecules have the ring structure characteristic of benzene, naphthylene, phenanthrene, anthracene, etc. For example, a C¢Hs aromatic structure is an “phenyl”, a ' CeH4* aromatic structure is an “phenylene”. An “arylalkyl” group is an alkyl group having an aryl group pendant therefrom; an “alkylaryl” is an aryl group having one or more alkyl groups pendant therefrom. = + -[0019} ----- As used herein, an “alkylene” includes linear, branched and cyclic hydrocarbon ~~ radicals deficient by two hydrogens. Thus, —CH,— (“methylene”) and ~CH,CHx— (“ethylene”) are examples of alkylene groups. Other groups deficient by two hydrogen radicals include “arylene” and “alkenylene”.

[0020] As used herein, the phrase “heteroatom” includes any atom other than carbon and hydrogen that can be bound to carbon, and in one embodiment is selected from the group consisting of B, Al, Si, Ge, N, P, O, and S. A “heteroatom-containing group” is a hydrocarbon radical that contains a heteroatom and may contain one or more of the same or different heteroatoms, and from 1 to 3 heteroatoms in a particular embodiment. Non-limiting examples of heteroatom-containing groups include radicals of imines, amines, oxides, phosphines, ethers, ketones, oxoazolines heterocyclics, oxazolines, thioethers, and the like.

[0021] As used herein, an ‘“alkylcarboxylate”, “arylcarboxylate”, and “alkylarylcarboxylate” is an alkyl, aryl, and alkylaryl, respectively, that possesses a carboxyl group in any position. Examples include C¢HsCH,C(O)O", CH3C(0)O, etc.

[0022] 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, the moieties : selected from such groups as halogen radicals (esp., Cl, F, Br), hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, ' naphthyl groups, C, to Co alkyl groups, C; to Cy alkenyl groups, and combinations thereof,

Examples of substituted alkyls and aryls includes, but are not limited to, acyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- and dialkyl-

carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals, and combinations thereof. ‘

[0023] As used herein, structural formulas are employed as is commonly understood in the chemical arts; lines (“—"") 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, as these lines and phrases are meant to represent a “chemical bond”; a “chemical bond” defined as an attractive force between atoms that is strong enough to permit the combined aggregate to function as a unit, or “compound”.

[0024] 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.

[0025] 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.

[0026] 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 are essentially the same type of polymer, for example, polypropylene or polyethylene.

_7 = ! [0027] As used herein, the term “productivity” means the weight of polymer produced per weight of the catalyst used in the polymerization process (e.g., grams polymer/gram catalyst).

[0028] As used herein, the term “dehydrated” is understood as having the broadest definition 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--suppert particle, from “which a majority "of the = ~~ contained/adsorbed water has been removed.

[0029] As used herein, the term “salt” means a chemical compound that may be formed by a chemical reaction of an acid and a base.

[0030] As used herein, the term “fluoriding agent” is defined as any inorganic compound or combination of two or more inorganic compounds capable of forming at least one bonding association between a fluorine or fluorine-containing moiety and a target compound. ) The fluoriding agent can be any inorganic compound or combination of two or more inorganic compounds that includes one or more fluorine atoms, and more particularly, a fluorinated inorganic salt. The “target compound” can be any compound capable of forming a bonding association with a fluorine ion, examples of which include Group 3 to 12 metals and metal compounds, and desirably, Group 3 to 6 metallocene compounds. Non-limiting examples of “fluorine-containing moieties” include fluorine ions and radicals.

[0031] As used herein, the term “product yield” means the weight of product produced per weight of maximum product possible (e.g., grams fluorinated catalyst per gram of theoretical fluorinated catalyst).

Process for Making a Fluorinated Catalyst Compound ; [0032] Embodiments of the invention include a process of producing a fluorinated catalyst compound, and in particular, a fluorided metallocene catalyst component. The fluorided metallocene itself is described in more detail below. The fluorided metallocene catalyst component can be, for example, any one of the catalysts described in greater detail below, or the “second catalyst component” of the bimodal catalyst. The fluorided catalyst compound is preferably a metallocene type compound having the general formula (Cp(R)p)mMX,F; (Which can include, for example, a partially fluorinated metallocene), wherein

Cp is a cyclopentadienyl ligand or ligand isolobal to cyclopentadienyl (as described further below) that can be substituted in any position by a group R as set out below, M is a Group 4, 5, or 6 transition metal in a particular embodiment, X is an anionic ligand such as a halogen, carboxylate, acetylacetonate, alkoxide, hydroxide, or oxide; p is an integer from 0 to 10, m is : an integer from 1 to 3, nis an integer from 0 to 3, and r is an integer from 1 to 3; ma particutar: embodiment, m is 2, n is 0 and r is 2. If m is 2, the Cps may be bridged by a group (A) as described further below.

[0033] The process includes contacting a metallocene catalyst compound with a fluoriding agent, and more particularly, a fluorinated inorganic salt, for a time sufficient to form the fluorided metallocene catalyst compound. The metallocene catalyst compound preferably has the same general formula as the desired fluorinated metallocene compound, with the exception that the one or more leaving groups X are an anionic ligand (e.g., chlorine or bromine) rather than fluorine. The metallocene compound that is contacted with the fluoriding agent may be commercially available, or may be prepared by methods known to one skilled in the art.

[0034] The metallocene compound may include a cyclopentadieny! ligand or ligand isolobal to Cp, either substituted or unsubstituted. The amount of substitution on the Cp may affect the yield of the fluorinated metallocene compound. Therefore, at least one Cp of the metallocene is substituted in one embodiment, and two Cps are substituted in another embodiment, wherein the metallocene is a sandwich metallocene as set out below. In a particular embodiment, the substituent group (R) is not an aryl group such as phenyl, indenyl or fluorenyl. In at least certain embodiments, it has been discovered that benzene substituent ‘ groups correspond to reduced product yields. For example, when R is indenyl, the product yield may be as low as zero. Preferably, the substituent groups include hydrocarbyl groups. In a preferred embodiment, alkyl substitution results in surprisingly high yields, for example, 95% or more.

[0035] In one embodiment, the fluoriding agent is a fluorinated inorganic salt or ’ combination of salts described by the general formula (a):

GING (a) wherein a is a cationic species selected from the group consisting of Group 1 and 2 cations, anilinium and substituted versions thereof, and NH.", NH;R, NH;R;, and NHR;* + = + ---- wheretr R is selected from the group consisting of hydride, chloride, Cy fo Cjp alkyland ~~

Ce to Cy; aryls;

B is an anionic species selected from the group consisting of fluorine ions and compounds comprising fluorine and one or more elements selected from the group consisting of hydrogen, silicon, carbon, phosphorous, oxygen, aluminum and boron; and aandb are integers from 1 to 10.

[0036] In a particular embodiment, the fluorinated inorganic salt is a compound characterized in that it is capable of generating fluoride ions when contacted with water or other protic diluent. Non-limiting examples of the fluorinated inorganic salt include (NH,);AlFs NH,HF,, NaF, KF, NHF, (NHy), SiFs and combinations thereof.

[0037] The fluorinated inorganic salt compound may include a fluorinated inorganic salt mixture. The fluorinated inorganic salt compound is preferably soluble or partially soluble in a diluent. Therefore, the mixture may include the fluorinated inorganic salt and a diluent, that is, the fluorinated inorganic salt may be dissolved in a diluent prior to contacting the metallocene catalyst compound. The diluent may include an organic diluent. In a particular embodiment, the diluent is water or water in combination with some other polar diluent that is miscible with water (e.g., ethers, ketones, aldehydes, etc). In another embodiment, the diluent ! is any desirable protic medium. In a particular embodiment, the fluorinated inorganic salt is combined with a diluent that is at least 50 wt% water, and at least 60 wt% water in another embodiment, and at least 70 wt% water in yet another embodiment, and at least 80 wt% water

( C in yet another embodiment, and at least 90 wt% in a particular embodiment, and at least 99 wt% water in a more particular embodiment.

[0038] The metallocene compound that is contacted with the fluoriding agent may be initially charged in an inert or non-protic diluent. The inert diluent may include one of, or a mixture of, aliphatic and aromatic hydrocarbons or a halogenated solvent. Suitable hydrocarbons include substituted and unsubstituted aliphatic hydrocarbons and substituted and unsubstituted aromatic hydrocarbons: Ina particular embodiment, the inert diluent is selected from the group consisting of C3 to Cp hydrocarbons and C; to Cjp halogenated hydrocarbons and mixtures thereof in a particular embodiment. Non-limiting examples of suitable inert diluents include hexane, heptane, octane, decane, toluene, xylene, dichloromethane, dichloroethane, chloroform and 1-chlorobutane.

[0039] In a particular embodiment of the method of fluoriding metallocenes described herein, the fluorinated inorganic salt combined with a protic diluent is reacted with the metallocene combined with an inert diluent. In a more particular embodiment, the fluorinated inorganic salt in at least 50% water is combined with the metallocene to be fluorided dissolved/suspended in a hydrocarbon or halogenated hydrocarbon diluent. The combined reactants may form two or more phases in contact with one another. The fluoriding reaction then takes place under desirable mixing and temperature conditions.

[0040] In embodiments of the fluoriding step wherein the fluoriding agent is immiscible or only partially miscible with the diluent, it is within the scope of the invention to use a reagent that will assist the transport of the fluoriding agent to the alkylated catalyst '5 component or the diluent phase in which the alkylated catalyst component exists, or assist in the reaction between the fluoriding agent and alkylated catalyst component. Such reagents— phase-transfer catalysts—are known in the art and are used in reactions wherein, for example, ' an aqueous or polar diluent phase is in contact with a non-polar or hydrocarbon diluent phase, and the reactants are separated as such. Non-limiting examples of such phase-transfer catalysts 0 include quaternary ammonium salts (e.g., quaternary ammonium bisulfate), crown ethers, and others common in the art.

(J

[0041] Depending on the desired degree of substitution, the ratio of fluorine (of the . fluoriding agent) to metallocene combined to react is from 1 equivalent to 20 equivalents in one embodiment, and from 2 to 10 equivalents in another embodiment, and from 2 to 8 ) equivalents in yet another embodiment, and from 2 to 5 equivalents in yet another embodiment, wherein a desirable range comprises any combination of any upper limit with any lower limit.

While excess fluorinated inorganic salt may not be detrimental, the molar ratio of the reactants is preferably determined by the number of anionic ligands to be substituted in the metallocene -— compound, that is, the number of anionic ligands to be replace by fluorine or fluoride atoms. In co a particular embodiment, the number of anionic ligands to be substituted is 2.

[0042] Stated another way, the desired amount of fluoriding agent, based on the equivalents of fluorine in the fluoriding agent, that is combined with the metallocene catalyst compound ranges from 1, or 2, or 3,or4,or Sto 6, or 7,0r 8, or 10, or 12, or 14 or 15 or 18 or 20, wherein a desirable range comprises any combination of any upper limit with any lower limit described herein. In another embodiment, the desired amount of fluoriding agent, based on the equivalents of fluoriding agent as a whole, ranges from 1, or 2, or 3, or 4 to 5 or 6, or 7, or 8, or 9, or 10, wherein a desirable range comprises any combination of any upper limit with any lower limit described herein.

[0043] The fluorinated inorganic salt may be reacted with the metallocene compound by vigorously stirring the compounds. The reaction may occur at any temperature that affords the desired mono, di or trifluorided metallocene, including temperatures of from —80 °C to 120 °C in one embodiment, and from 0 to 100 °C in a more particular embodiment, and from 10 to 60°C in yet a more particular embodiment, and from 15 to 40°C in yet a more particular embodiment. At those temperatures, reaction times of 0.05 hour to 8 hours are sufficient to form a fluorinated metallocene compound, but routine experimentation may be desirable to arrive at an optimum temperature. Generally, the reaction time is dependent upon the amount of reactants reacted. In one embodiment, the reaction time is from 0.1 hour to 3 hours.

[0044] The diluent, along with reaction by-products, can be removed from the mixture in a conventional manner, such as by evaporation or filtering, to obtain the dry, fluorinated metallocene compound. For example, the fluorided metallocene may be dried in the presence of magnesium sulfate. The filtrate, which contains the fluorinated metallocene compound in high purity and yield, can without further processing be directly used in the polymerization of ) olefins if the solvent is a hydrocarbon.

[0045] Contacting the metallocene compound with the fluorinated inorganic salt, an aqueous fluorinated inorganic salt, results in a product yield of 50% or more in a particular embodiment. The product yield is 80% or more in yet a more particular embodiment. The product yield is 90% or more in yet a more particular embodiment. Unexpectedly, contacting the metallocene compound with the aqueous solution of fluorinated inorganic salt results in a fluorided metallocene compound having high productivities.

Bimetallic Catalyst

[0046] As used herein, the term “bimetallic catalyst” or “bimetallic catalyst system” refers to two or more catalyst components used in combination with at least one activator, and optionally a support material, that is useful in polymerizing olefins. The “supported bimetallic catalyst” or “supported bimetallic catalyst composition” refers the 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 of the invention includes two catalyst components. In a more particular embodiment, the bimetallic catalyst component includes a “first catalyst component” and a “second catalyst component”.

[0047] As used herein, the term “first catalyst component” refers to any catalyst component other than the second catalyst component. Preferably, the first catalyst component is a non-metallocene catalyst component, examples of which include titanium or vanadium based Ziegler-Natta catalysts compounds as described further herein.

[0048] As used herein, the term “non-metallocene compound” refers any catalyst that is neither a metallocene nor one of the metallocene-type catalyst compounds identified below.

[0049] As used herein, the term “second catalyst component” refers to any catalyst that is different from a first catalyst component, a metallocene catalyst component in a particular

® embodiment. In a particular embodiment, the second catalyst component includes a fluorided metallocene component which comprises at least one fluoride ion leaving group or fluorine containing group.

[0050] Certain embodiments of the present invention involve contacting monomers with a bimetallic catalyst component, also referred to herein as simply a bimetallic catalyst. In a particular embodiment, each different catalyst compound that comprises the bimetallic

To 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 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 may be introduced into the polymerization reactor sequentially in any order, alternately in parts, or simultaneously.

[0051] 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, polymerization in the presence of the first and second catalyst components provides a bimodal polyolefin composition that includes a low molecular weight component and a high molecular weight component. The two catalyst components reside on a single support particle in a particular embodiment, and they can be affixed to the support in a variety of ways.

[0052] In one embodiment, an “enhanced silica” is prepared as described herein and constitutes the support; the first catalyst component is a non-metallocene compound that is first combined with the enhanced silica, to provide a supported non-metallocene composition; the supported non-metallocene composition is combined with the second catalyst component, for example, a fluorided metallocene (a metallocene having at least one fluorine ion leaving group), resulting in a fluorinated bimetallic catalyst composition having enhanced productivity when used in production of a bimodal polyolefin composition.

[0053] Various methods of affixing two different catalyst components (albeit a different ) combination of catalysts) to a support can be used. In general, 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, and drying the resulting product that includes the first and second catalyst components and recovering a bimetallic catalyst composition. oT To Co TTT

First Catalyst Component

[0054] As noted above, the bimetallic catalyst composition includes a first catalyst component, which is (or includes) 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, in ZIEGLER

CATALYSTS 363-386 (G. Fink, R. Muthaupt and H.H. Brintzinger, eds., Springer-Verlag 1995).

Examples of such catalysts include those comprising TiCly and other such transition metal oxides and chlorides.

[0055] The first catalyst component is combined with a support material in one 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 C;-Cy2 alkyl groups, or C4-Cyo alkyl groups, or C;-Cy alkyl groups. In at least one specific embodiment, the organomagnesium compound is dibutyl magnesium. In one embodiment, the amount of organomagnesium compound included in the silica slurry is only that which will be deposited,

Claims (15)

© WO 2004/022230 © PCT/US2003/025280 CLAIMS What is claimed is: oo

1. A process of producing a fluorided catalyst compound, comprising contacting a metallocene catalyst compound with an fluorinated inorganic salt to form a fluorinated metallocene catalyst compound.

2. °° The process of Claim 1; wherein the fluorinated inorganic -salt-is- characterized by ~~ generating fluoride ions when contacted with a diluent that is at least 50 wt% water.

3. The process of Claim 1, wherein the fluorinated inorganic salt is described by the general formula: [a]a[Blos . wherein o is a cationic species selected from the group consisting of Group 1 and 2 cations, anilinium and substituted versions thereof, and NH", NH;R, NHR, and NHR," wherein R is selected from the group consisting of hydride, chloride, C, to Co alkyl and Cg to Cy; aryls; B is an anionic species selected from the group consisting of fluorine ions and moieties comprising fluorine and one or more elements selected from the group consisting of "hydrogen, silicon, carbon, phosphorous, oxygen, aluminum and boron; and a and b are integers from 1 to 10.

4. The process of Claim 1, wherein the inorganic salt is selected from the group consisting . of (NH,); AlFs, NH HF,, NaF, KF, NH,F, (NH,):SiF¢ and combinations thereof.

5. The process of Claim 1, wherein the metallocene compound is described by the formulae:

: | ( C Cp*Cp°MXa, Cp*MX, or Cp*(A)CpPMX, wherein M is a Group 4, 5 or 6 atom; Cp” and Cp® are each bound to M and are independently selected from the group consisting of cyclopentadienyl ligands, substituted cyclopentadienyl ligands, ligands isolobal to cyclopentadienyl and substituted ligands isolobal to

- . . - - - . cyclopentadienyl; FR - PE mime ee amie fm mime mm = men ema semen mee - (A) is a divalent bridging group bound to both cpt and Cp® selected from the group consisting of divalent C; to Cy hydrocarbyls and C; to Cy heteroatom containing hydrocarbonyls; wherein the heteroatom containing hydrocarbonyls : comprise from one to three heteroatoms; X is an anionic leaving group selected from the group consisting of chlonde ions, bromide ions, carboxylates, acetylacetonates, and alkoxides; and n is an integer from 1 to 3.

6. The process of Claim 1, wherein the metallocene compound is described by the formulae: Cp*CpPMX, or CpA(A)CpPMX, wherein M is zirconium or hafnium; ‘ Cp” and Cp® are each bound to M and are independently selected from the group consisting of substituted cyclopentadienyl! ligands, substituted indenyl! ligands, substituted tetrahydroindenyl ligands, substituted fluorenyl ligands, and heteroatom derivatives of each; wherein the substituent groups are selected from

. the group consisting of C; to Cig alkyls and halogens;

(A) is a divalent bridging group bound to both Cp” and Cp® selected from the group consisting of divalent C; to Cy hydrocarbyls and C; to Cy heteroatom containing hydrocarbonyls; wherein the heteroatom containing hydrocarbonyls comprise from one to three heteroatoms; X is an anionic leaving group selected from the group consisting of chloride ions, bromide ions, carboxylates, acetylacetonates, and alkoxides; and : n is an integer from 1 to 3. Comm me :

7. The process of Claim 6, wherein at least one Cp is substituted.

8. The process of Claim 6 wherein at least one Cp is disubstituted.

9. The bimetallic catalyst composition of Claim 6, wherein at least one Cp has from 2 to 5 substitutions.

10. The bimetallic catalyst composition of Claim 6, wherein the substituent groups are selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, and tert-butyl.

11. The bimetallic catalyst composition of Claim 1, wherein the fluorided metallocene is further combined with an inorganic oxide is dehydrated at a temperature of greater than 830°C.

12. The process of Claim 1, wherein the fluorinated metallocene has a productivity of at least 3,000 g polymer/g catalyst towards slurry or gas phase ethylene polymerization process at a temperature of from 50°C to 120°C.

13. The process of Claim 1, wherein contacting the metallocene with the fluorinated inorganic salt comprises contacting the metallocene compound with from 2 to 20 equivalents of the fluorinated inorganic salt based on the number of equivalents of fluorine atom.

14. The process of Claim 1, wherein the metallocene catalyst component is in contact with a hydrocarbon or halogenated hydrocarbon diluent. ‘

15. The process of Claim 1, wherein the fluorinated inorganic salt is in contact with a diluent comprising at least 10 wt% water.