ZA200501168B

ZA200501168B - Bimodal polyolefinproduction process and films therefrom

Info

Publication number: ZA200501168B
Application number: ZA200501168A
Authority: ZA
Inventors: Chi-I Kuo; Pradeep P Shirodkar; Porter C Shannon; Steven K Ackerman; Laughlin G Mccullough; Fred D Ehrman; Robert L Santana; Daniel G Oneil
Original assignee: Univation Tech Llc
Priority date: 2002-09-04
Filing date: 2005-02-09
Publication date: 2006-09-27

Description

( : ® WO 2004/022607 PCT/US2003/025281

BIMODAL POLYOLEFIN PRODUCTION PROCESS

, AND FILMS THEREFROM

FIELD OF INVENTION

[0001] The present invention relates to bimodal polyolefin production, and more particularly, to bimodal polyolefins in producing films, wherein the bimodal polyolefin is produced in a single reactor using a bimetallic catalyst in a desirable embodiment.

BACKGROUND

[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; WO 97/07141; DE 43 32 009 Al; EP-A2 0 200 351; EP-Al 0 705 849; 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)2(n’-CsMes)Zr(p-

F)SnMe;Cl], DALTON, 1983 (1996); A. Herzog, et al, Reactions of (17-CsMes)ZrF;, (r7-

CsMe EYZrFs, (17-CsM45),ZrF,, (17'-CsMes)HfFs, and (1’-CsMes)TaF, 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. It ‘would be desirable to further improve upon this system, especially for bimodal gas phase polymerization processes. The present invention is directed towards solving this and other problems.

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SUMMARY

(0004] The present invention provides a method for bimodal polyolefin production, . preferably using bimetallic catalysts, and polyolefins films made from bimodal polyolefin compositions. At least one embodiment of the invention is directed to a process of producing a ' bimodal polyolefin composition that includes contacting monomers with a supported bimetallic catalyst composition for a time sufficient to form a bimodal polyolefin composition; wherein the supported bimetallic catalyst includes a first catalyst component and a second catalyst component that includes a metallocene catalyst compound having at least one fluoride or fluorine containing leaving group.

[0005] Another specific embodiment of the invention is directed to a process of producing a bimodal polyolefin composition comprising contacting monomers with a supported bimetallic catalyst composition for a time sufficient to form the bimodal polyolefin composition that includes a high molecular weight polyolefin component and a low molecular weight polyolefin component; wherein the supported bimetallic catalyst includes a first catalyst component that includes a fluorinated metallocene represented by the formula Cp;MF; wherein

Cp is a substituted or unsubstituted cyclopentadieny! ring or derivative thereof, M is a Group 4, 5, or 6 transition metal and a support material comprising silica dehydrated at a temperature of 800 °C or more.

[0006] Yet another specific embodiment of the invention is directed to a process of producing a bimodal polyolefin composition, including providing a particulate support material comprising silica; heating the particulate support material to a temperature of 800 °C or more for a time sufficient to form a dehydrated support material including dehydrated silica; combining the dehydrated support material with a non-polar hydrocarbon to provide a support slurry; providing a first catalyst component that is a non-metallocene catalyst; providing a second catalyst component that includes a metallocene catalyst compound having at least one . fluoride or fluorine containing leaving group; combining the support slurry with the first and second catalyst components to form a supported bimetallic catalyst composition; and contacting monomers with the bimetallic catalyst composition for a time sufficient to form a bimodal polyolefin composition having a density of from 0.86 g/em’ to 0.97 g/ cm’, a

( ( molecular weight distribution of from 5 to 80, a I; of from 0.01 dg/min to 50 dg/min, and a ' melt index ratio of from 40 to 500. :

[0007] In certain aspects, a film made from one or more of the bimodal polyolefin compositions disclosed herein has a Dart Drop Impact F50 Value of at least 100 [g] on 25.4 micron film and 75 [g] on 12.5 micron film.

[0008] In certain aspects, a film made from one or more of the bimodal polyolefin compositions disclosed herein has an MD Tear value of at least 0.4 g/micron on 25.4 micron film and at least 0.2 g/micron on 12.5 micron film.

[0009] In certain aspects, a film made from one or more of the bimodal polyolefin compositions disclosed herein has a TD Tear value of at least 1.5 g/micron on 24.5 micron film and 1.0 g/micron on 12.5 micron film. :

[0010] In particular embodiments, the support material useful in the process of the invention has been enhanced, in that it includes silica dehydrated at a temperature of 800°C or more. In a more particular embodiment, the support material includes silica dehydrated at a temperature of 830 °C or more. In yet a more particular embodiment, the support matenal includes silica dehydrated at a temperature of 875 °C or more.

DETAILED DESCRIPTION

General Definitions

[0011] 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).

[0012] 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. }

[0013] 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.

[0014] 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.

[0015] As used herein, the term “fluorinated 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.

[0016] 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.

[0017] 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

CH;CH;- group (“ethyl”) are examples of alkyls.

[0018] 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. :

[0019] As used herein, “aryl” groups includes phenyl, naphthyl, pyridyl and other radicals whose molecules have the ring structure characteristic of benzene, naphthylene,

Py WO 2004/022607 | ( PCT/US2003/025281 phenanthrene, anthracene, etc. For example, a C¢Hs aromatic structure is an “phenyl”, a ‘ C¢H,* 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.

[0020] As used herein, an “alkylene” includes linear, branched and cyclic hydrocarbon radicals deficient by two hydrogens. Thus, -CHy— (“methylene”) and -CH,CHy— (“ethylene”) are examples of alkylene groups. Other groups deficient by two hydrogen radicals include “arylene” and “alkenylene”. {0021} 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.

[0022] 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 CsHsCH,C(0)O", CH3C(0)O;, etc.

[0023] 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 Cio alkyl groups, C; to Co alkenyl groups, and combinations thereof.

Examples of substituted alkyls and aryls includes, but are not limited to, acyl radicals, - atkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoy! radicals, alkyl- and dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals, and combinations thereof.

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[0024] 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”.

[0025] 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.

[0026] 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.

[0027] 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.

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PY WO 2004/022607 | PCT/US2003/025281 -7 =

[0028] 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).

[0029] 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 support particle, from which a majority of the contained/adsorbed water has been removed.

Gas-phase polymerization using bimetallic catalysts comprising a fluorided metallocene catalyst component

[0030] The present invention provides a process for producing a bimodal polyolefin composition comprising: contacting olefin monomers with a bimetallic catalyst composition to form a bimodal polyolefin composition; wherein the bimetallic catalyst composition comprises: a first catalyst component; and metallocene catalyst compound having at least one fluoride or fluorine containing leaving group. In a particular embodiment, the bimetallic catalyst is supported. The bimetallic catalyst, each of its components, and the method of polymenzation are set out in greater detail below.

[0031] In one aspect of the invention, the method of making bimodal polymers is characterized in that the monomers are contacted with the bimetallic catalyst in a single reactor vessel and form the bimodal polyolefin composition in the same reactor vessel.

[0032] The present invention also provides a bimodal film composition comprising a polyolefin having a density of from 0.86 g/em’ to 0.97 g/cm’, a molecular weight distribution of from 5 to 80, a melt index of from 0.01 dg/min to 50 dg/mun, and a melt index ratio of from 40 to S00. The film composition, or film, is formed from the bimetallic catalyst of the : invention, and has certain desirable features as set out further below. :

Bimetallic Catalyst

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[0033] 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”. 10034) As used herein, the term “first catalyst component” refers to any catalyst component other than the second catalyst component. Preferably, the first catalyst component 's a non-metallocene catalyst component, examples of which include titanium or vanadium based Ziegler-Natta catalysts compounds as described further herein.

[0035] As used herein, the term “non-metallocene compound” refers any catalyst that 1s neither a metallocene nor one of the metallocene-type catalyst compounds identified below. 10036] 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.

[0037] Certain embodiments of the present invention involve contacting monomers with the bimetallic catalyst component. In a particular 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 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

PY WO 2004/022607 PCT/US2003/025281 embodiment, each supported catalyst may be introduced into the polymerization reactor : sequentially in any order, alternately in parts, or simultaneously.

[0038] 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.

[0039] 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.

[0040] 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.

First Catalyst Component

[0041] 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. Mulhaupt and H.H. Brintzinger, eds., Springer-Verlag 1995).

Examples of such catalysts include those comprising TiCls and other such transition metal oxides and chlondes.

[0042] 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,-C;; alkyl groups, or C4-Cyg alkyl groups, or C4-Cg alkyl groups. Inat 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, physically or chemically, onto the support, for example, being bound to the hydoxy! groups on the support, and no more than that amount, since 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. Altematively, 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 range from 0.2 mmol/g to 2 mmol/g in one embodiment.

( ® WO 2004/022607 PCT/US2003/025281

[0043] Optionally, the organomagnesium compound-treated slurry is contacted with an electron donor, such as tetraethylorthosiloxane (TEOS) or an organic alcohol R”OH, where R” is a C;-C), alkyl group, or a C, to Cg alkyl group, or a C; to C4 alkyl group. In a particular embodiment, R”OH is n-butanol. The amount of alcohol used in 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.

[0044] The organomagnesium and alcohol-treated slurry is contacted with a non- metallocene transition metal compound. Suitable non-metallocene transition metal compounds are 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 (TiCly), vanadium tetrachloride (VCl;) and vanadium oxytrichloride (VOCl;), 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 may also be used. The amount of non-metallocene transition metal compound used is sufficient to give a transition metal to magnesium mol/mol ratio of from 0.3 to 1.5, or from 0.5 to 0.8. The diluent can then be removed in a conventional manner, such as by evaporation or filtering, to obtain the dry, supported first catalyst component.

[0045] The first and second catalyst components may be contacted with the support in any order. In a particular embodiment of the invention, the first catalyst component is reacted first with the support as described above, followed by contacting this supported first catalyst component with a second catalyst component. }

Process for Making a Fluorinated Catalyst Compound

[0046] 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 (or include) any fluorided metallocene catalyst component, but is preferably a fluorided metallocene catalyst component. The fluorided metallocene catalyst component can be, for example, any one of the catalysts described in greater detail below, or

( ( -12~ 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)mMXF, (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, n is an integer from O to 3, and r is an integer from 1 to 3.

[0047] 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.

[0048] The metallocene compound may include a cyclopentadienyl ligand or ligand isolobal to Cp, either substituted or unsubstituted. The amount of substitution on 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 i a preferred embodiment, alkyl substitution results in surprisingly high yields, for example, 95% or more. .

[0049] In one embodiment, the fluoriding agent is a fluorinated inorganic salt or combination of salts described by the general formula (a):

B (ala[Blbs (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;" wherein R is selected from the group consisting of hydride, chloride, C; to Cy alky! and

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 a and b are integers from 1 to 10.

[0050] 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, (NH), SiFs and combinations thereof.

[0051] 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 in yet another embodiment, and at least 90 wt% in a particular embodiment, and at least 99 wt% water in a more particular embodiment.

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[0052] 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. In a particular embodiment, the inert diluent is selected from the group consisting of C3 to Cs hydrocarbons and C; to Co 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.

[0053] 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. {0054] 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 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 include quaternary ammonium salts (e.g., quaternary ammonium bisulfate), crown ethers, and . others common in the art.

[0055] 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

Claims

( ( . , -68 — oo CLAIMS What is claimed is: .

1. A bimetallic catalyst composition comprising a fluorided metallocene catalyst ’ component, a non-metallocene catalyst component, and an activator, the catalyst components and activator supported on an inorganic oxide dehydrated at a temperature of greater than 800°C.

2. The bimetallic catalyst composition of Claim 1, wherein the fluorided metallocene compound is described by the formulas: Cp Cp®MX,, Cp"MX, or Cp*(A)Cp°MX, 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; (A) is a divalent bridging group bound to both Cp” and Cp® selected from the group consisting of divalent C, to C0 hydrocarbyls and C, to Cy heteroatom containing hydrocarbonyls; wherein the heteroatom containing hydrocarbonyls comprise from one to three heteroatoms; at least one X is a fluoride ion; and n is an integer from 1 to 3.

3. The bimetallic catalyst composition of Claim 1, wherein the metallocene compound is described by the formulas: Cp”Cp®MX,, or Cp™(A)Cp°MX,

Lo ( wherein M is zirconium or hafnium; Cp* and Cp® are each bound to M and are independently selected from the group consisting of substituted cyclopentadieny! ligands, substituted indenyl ligands, substituted tetrahydroindeny! ligands, substituted fluorenyl ligands, and heteroatom derivatives of each; wherein the substituent groups are selected from the group consisting of C, to Cg 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; at least one X is a fluoride ion; and nis an integer from 1 to 3. 4, The bimetallic catalyst composition of Claim 1, wherein at least one Cp is substituted.

5. The bimetallic catalyst composition of Claim 1, wherein at least one Cp is disubstituted.

6. The bimetallic catalyst composition of Claim 1, wherein at least one Cp has from 2 to 5 substitutions.

7. The bimetallic catalyst composition of Claim 1, wherein the substituent groups are selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- butyl, and tert-butyl.

8. The bimetallic catalyst composition of Claim 1, wherein the bimetallic catalyst also includes a Ziegler-Natta catalyst component.

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9. The bimetallic catalyst composition of Claim 8, wherein the Ziegler-Natta catalyst component comprises a compound selected from the group consisting of Group 4 and Group 5 . halides, oxides, oxyhalides, alkoxides, and mixtures thereof.

10. The bimetallic catalyst composition of Claim 1, wherein the inorganic oxide is dehydrated at a temperature of greater than 830°C.

11. The process of Claim 1, wherein the support material comprises silica dehydrated at a temperature of 870 °C or more.

12. The bimetallic catalyst composition of Claim 1, wherein the inorganic oxide is silica.

13. A process for producing a bimodal polyolefin composition comprising: contacting hydrogen and ethylene monomers with the supported bimetallic catalyst composition of Claim 1 to form a bimodal polyolefin composition.

14. The process of Claim 13, wherein the bimetallic catalyst has a productivity of at least 3000 grams polymer/gram catalyst.

15. The process of Claim 13, wherein the bimetallic catalyst has a productivity of at least 3500 grams polymer/gram catalyst.

16. The process of Claim 13, wherein from 0.01 wt. ppm to 200 wt. ppm of water is also contacted.

17. The process of Claim 13, wherein the first catalyst component is a Ziegler-Natta catalyst. .

18. The process of Claim 17, wherein the Ziegler-Natta catalyst component comprises a : compound selected from the group consisting of Group 4 and Group 5 halides, oxides, oxyhalides, alkoxides, and mixtures thereof.

( (

19. The process of Claim 13, wherein the supported bimetallic catalyst composition : includes a support material comprising a Group 13 or 14 inorganic oxide dehydrated at a temperature of from 800°C to 1000°C. ’

20. The process of Claim 13, wherein Cp* and Cp® are selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, and substituted versions thereof.

21. The process of Claim 13, wherein Cp” and Cp® are selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, and substituted versions thereof; characterized in that at least one of either Cp” or Cp® has at least one R group selected from C, to Cg alkyls.

22. The process of Claim 13, further comprising combining a comonomer selected from Cs to C,; olefins.

23. The process of Claim 13, further comprising combining a comonomer selected from the group consisting of 1-propene, 1-butene, 1-hexene and 1-octene.

24. The process of Claim 13, wherein the monomers are contacted with the supported bimetallic catalyst in a single reactor vessel and form the bimodal polyolefin composition in the same reactor vessel.

25. The process of Claim 13, wherein the bimetallic catalyst composition further comprises alumoxane.

26. The process of Claim 13, wherein the molar ratio of hydrogen to ethylene ranges from

0.001 to 0.015.

27. The process of Claim 13, further comprising the steps of: (a) providing a particulate support material comprising silica; (b) heating the particulate support material to a temperature of 800 °C or more for a time sufficient to form a dehydrated support material comprising dehydrated silica;

( ( (©) combining the dehydrated support material with a non-polar hydrocarbon to provide a support slurry; ) (d) providing a first catalyst component that includes a non-metallocene catalyst; (¢) providinga second catalyst component that includes a metallocene catalyst ’ compound having at least one fluoride or fluorine containing leaving group; $3) combining the support slurry with the first and second catalyst components to form a supported bimetallic catalyst composition; (g) contacting monomers with the bimetallic catalyst composition for a time sufficient to form a bimodal polyolefin composition; wherein the bimodal polyolefin composition has a density of from 0.86 g/cm’ to

0.97 g/cm’, a molecular weight distribution of from 5 to 80, a I; of from 0.01 dg/min to 50 dg/min, and a 11/1; of from 40 to 500.

28. A bimodal polyolefin composition of Claim 27, wherein the bimodal polyolefin composition has a density of from 0.86 g/cm’ to 0.97 g/cm’, a molecular weight distribution of from 5 to 80, a I; of from 0.01 dg/min to 50 dg/min, and a 1/1; of from 40 to 500.

29. A film made from the composition of Claim 28, wherein the film has a Dart Drop Impact F50 Value of at least 100 [g] on 25.4 micron film and 75 [g] on 12.5 micron film.

30. The film of Claim 29, wherein the film has an MD Tear value of at least 0.4 g/micron on 25.4 micron film and at least 0.2 g/micron on 12.5 micron film.

31. The film of Claim 29, wherein the film has a TD Tear value of at least 1.5 g/micron on

24.5 micron film and 1.0 g/micron on 12.5 micron film.

32. The film of Claim 29, wherein the polyolefin comprises ethylene derived units. . 33 The film of Claim 29, wherein the polyolefin comprises ethylene derived units and units derived from the group consisting of C3 to Cio olefins.

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34. The film of Claim 29, wherein the polyolefin comprises ethylene derived units and units . derived from the group consisting of C4 to Cg a-olefins.

35. The film of Claim 29, wherein the polyolefin has a molecular weight distribution of from 10 to 60.

36. The film of Claim 29, wherein the polyolefin has a I; of from 0.002 to 2 dg/min.

37. The film of Claim 29, wherein the polyolefin has a I; of from 1 to 10 dg/min.

38. The film of Claim 29, wherein the polyolefin has a bulk density of from 0.420 to 0.600 g/cm’.

39. A process for producing the bimodal polyolefin composition comprising the steps of: (a) contacting the catalyst composition of Claim 1, the fluorinated metallocene catalyst compound produced by contacting a metallocene catalyst compound with an fluorinated inorganic salt for a time sufficient to form a fluorinated metallocene catalyst compound; (b) isolating the fluorided metallocene catalyst compound; (c) combining the fluorided metallocene catalyst compound with an activator and ethylene monomers and optionally a support at from 50°C to 120°C; and (d) isolating polyethylene.

40. The process of Claim 39, wherein the fluorided metallocene, activator and support are also combined with a Ziegler-Natta catalyst comprising titanium halide.

41. The process of Claim 39, wherein the fluorided metallocene, activator and support are combined and isolated prior to combining with ethylene monomers.

42. The process of Claim 39, wherein the fluorinated inorganic salt is characterized by generating fluoride ions when contacted with a diluent that is at least 50 wt% water.

43. The process of Claim 39, wherein the fluorinated inorganic salt is described by the general formula: [aJa[Bls 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;" wherein R is selected from the group consisting of hydride, chloride, C, to Cyo alkyl and Cg to C,; aryls; B is an anionic species selected from the group consisting of fluorine ions and moieties comprising fluorine and one or more clements selected from the group consisting of hydrogen, silicon, carbon, phosphorous, oxygen, aluminum and boron; and a and b are integers from 1 to 10.

44. The process of Claim 39, wherein the inorganic salt is selected from the group consisting of (NH,);AlFs, NH,HF,, NaF, KF, NH4F, (NH,):SiFs and combinations thereof.