Symmetrical zirconium metallocenes with isobutylcyclopentadienyl ligands.

Abstract

Embodiments of the present disclosure relate to symmetrical zirconium metallocenes having isobutylcyclopentadienyl ligands, compositions comprising symmetrical zirconium metallocenes having isobutylcyclopentadienyl ligands, and methods utilizing compositions comprising symmetrical zirconium metallocenes having isobutylcyclopentadienyl ligands.

Description

[Technical Field]

[0001] SUMMARY OF THE DISCLOSURE Embodiments of the present disclosure relate to symmetric zirconium metallocenes having isobutylcyclopentadienyl ligands, catalyst compositions comprising symmetric zirconium metallocenes having isobutylcyclopentadienyl ligands, methods for making and using the same, and polyolefins made thereby. [Background technology]

[0002] Metallocenes can be used in a variety of applications, including polymerization catalysts. Polymers can be utilized in many articles, including, among others, films. Polymers can be formed by reacting one or more monomers in a polymerization reaction. The industry continues to focus on developing new and improved materials and / or processes that can be utilized in growth media. Summary of the Invention

[0003] The present disclosure provides various embodiments, including the following.

[0004] A symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand represented by structure (I):

[0005] [ka] A symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand, wherein each X is independently a leaving group.

[0006] A metallocene catalyst composition comprising a symmetrical zirconium metallocene having an isobutylcyclopentadienyl ligand and an activator.

[0007] A method for producing a metallocene catalyst composition comprising contacting a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand with an activator.

[0008] A method for producing a polyolefin polymer, comprising polymerizing at least one olefin monomer with a metallocene catalyst composition to produce the polyolefin polymer. [Brief explanation of the drawings]

[0009] [Figure 1] 1 shows a data plot utilized to determine the Molecular Weight Comonomer Distribution Index (MWCDI) according to some embodiments of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0010] Symmetric zirconium metallocenes having isobutylcyclopentadienyl ligands are discussed herein. Advantageously, these symmetric zirconium metallocenes having isobutylcyclopentadienyl ligands can be utilized, for example, to produce catalyst compositions. These catalyst compositions can be utilized to produce polymers having improved, i.e., higher, molecular weight comonomer distribution index (MWCDI) compared to other polymers produced from other metallocenes. These polymers are desirable for many applications, including, particularly, films. Therefore, providing improved MWCDIs is advantageous. Such polymers are advantageous for many applications. In addition, these catalyst compositions can be utilized to produce polymers having improved, i.e., higher, comonomer incorporation (C6 wt%) compared to polymers produced from other metallocenes.

[0011] Symmetric zirconium metallocenes with isobutylcyclopentadienyl ligands can also be used to provide polymers with improved reverse short-chain branching distributions, as discussed herein. A defining characteristic of polymers such as poly(ethylene-co-1-alkene) resins is their short-chain branching distribution (SCBD), or comonomer distribution. For improved product performance in many applications, it is desirable to have a reverse SCBD or reverse comonomer distribution, in which the weight percent (wt%) of comonomer in the polymer increases as the molecular weight (MW) of the polymer chain increases. This is also referred to as a polymer with a broad orthogonal composition distribution (BOCD). Such distributions are typically obtained using a dual-reactor configuration and a single or dual-catalyst process. In a dual-reactor process, a single catalyst can be used to produce a high-MW, low-density component (with a higher comonomer wt%) and a low-MW, high-density component (with a lower comonomer wt%) in separate reactors through independent process control in the two reactors. The result is a bimodal resin with a reverse SCBD. In the case of a dual catalyst single reactor process, one catalyst produces a high MW low density component while the other forms a low MW high density component, resulting in a bimodal product with an inverse SCBD.

[0012] A more desirable method for obtaining polymers with reverse SCBD is to use a single catalyst capable of producing such BOCD resins in a single reactor. The disclosed symmetric zirconium metallocenes with isobutylcyclopentadienyl ligands, as discussed herein, provide the ability to produce, in a single reactor, polymers with improved BOCD resins, particularly polymers that have a measurably greater tendency for comonomers to chain to higher MW fractions and maintain significant BOCD properties over a wide range of process conditions. Additionally, there is a need in the industry for low melt index resins with broad molecular weight distributions and high BOCD compositions for film and other applications. Without being bound by theory, it is believed that the isobutyl groups of the disclosed symmetric zirconium metallocenes provide primary C(sp) groups available for CH activation. 3Increasing the number of )-H bonds, thereby increasing the frequency of this reaction, enhances the propensity of symmetric hafnium metallocene catalysts to be multi-sited and produce polymers with BOCD.

[0013] A symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand can be represented by structure (I).

[0014] [ka] Each X is independently a leaving group. As shown in structure (I), the upper cyclopentadienyl ring is substituted with an isobutyl ligand, and the lower cyclopentadienyl ring is substituted with another isobutyl ligand. Because one of both cyclopentadienyl rings is substituted with a respective isobutyl ligand, the metallocene may be referred to as a symmetrical metallocene.

[0015] Embodiments of the present disclosure provide that X is a leaving group. One or more embodiments provide that X is selected from alkyl, aryl, hydride, and halogen. One or more embodiments provide that X is selected from halogen, (C1-C5) alkyl, CH2SiMe3, and benzyl. One or more embodiments provide that X is selected from alkyl and halogen. One or more embodiments provide that X is Cl. One or more embodiments provide that X is methyl.

[0016] Examples of X include halogen ions, hydrides, (C1-C 12 ) Alkyl, (C2-C 12 ) alkenyl, (C6-C 12 ) Aryl, (C7-C 20 Alkylaryl, (C1-C 12 )Alkoxy, (C6-C 16 )aryloxy, (C7-C8)alkylaryloxy, (C1-C 12 ) Fluoroalkyl, (C6-C 12 ) fluoroaryl, and (C1-C12 ) heteroatom-containing hydrocarbons, and their substituted derivatives. One or more embodiments include hydrides, halides, (C1-C6) alkyls, (C2-C6) alkenyls, (C7-C 18 Alkylaryl, (C1-C6)alkoxy, (C6-C 14 ) Aryloxy, (C7-C 16 ) alkylaryloxy, (C1-C6) alkyl carboxylate, (C1-C6) fluorinated alkyl carboxylate, (C6-C 12 ) Aryl carboxylate (C7-C 18 ) alkylaryl carboxylate, (C1-C6) fluoroalkyl, (C2-C6) fluoroalkenyl, and (C7-C 18 )fluoroalkylaryl. One or more embodiments include hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl, fluoromethyl, and fluorophenyl. One or more embodiments include (C1-C 12 ) Alkyl, (C2-C 12 ) alkenyl, (C6-C 12 ) Aryl, (C7-C 20 ) Alkylaryl, substituted (C1-C 12 ) Alkyl, substituted (C6-C 12 ) Aryl, substituted (C7-C 20 ) alkylaryl, and (C1-C 12 ) Heteroatom-containing alkyl, (C1-C 12 ) heteroatom-containing aryl, and (C1-C 12 ) heteroatom-containing alkylaryl. One or more embodiments include chloride, fluoride, (C1-C6) alkyl, (C2-C6) alkenyl, (C7-C 18 ) alkylaryl, halogenated (C1-C6) alkyl, halogenated (C2-C6) alkenyl, and halogenated (C7-C 18) alkylaryl. One or more embodiments include fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyl (mono-, di-, and trifluoromethyl), and fluorophenyl (mono-, di-, tri-, tetra-, and pentafluorophenyl).

[0017] Other non-limiting examples of X groups include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon groups having 1 to 20 carbon atoms, fluorinated hydrocarbon groups such as -CF (pentafluorophenyl), fluorinated alkyl carboxylates such as CF C(O)O-, hydrides, 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, ethoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, and dimethylphosphide groups, among others. In one embodiment, two or more Xs form part of a fused ring or ring system. In one or more embodiments, X can be a chloride ion, a bromide ion, a (C1-C2) ion, a methyl ... 10 ) Alkyl, (C2-C 12 ) may be a leaving group selected from the group consisting of alkenyl, carboxylate, acetylacetonate, and alkoxide. In one or more embodiments, X is methyl.

[0018] The isobutylcyclopentadienyl ligand symmetric zirconium metallocenes discussed herein can be prepared by contacting a zirconium complex with an alkali metal complex to produce the isobutylcyclopentadienyl ligand symmetric zirconium metallocene. The symmetric zirconium metallocenes discussed herein can be prepared by processes using, for example, conventional solvents, reaction conditions, reaction times, and isolation procedures utilized to prepare known metallocenes.

[0019] The alkali metal complex may be represented by the following structure:

[0020] [ka] where M' is lithium, sodium, or potassium, and R 1 is an isobutyl group.

[0021] One or more embodiments provide that the zirconium complex can be zirconium tetrachloride.

[0022] One or more embodiments provide a method of producing a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand (e.g., where each X is Cl) comprising contacting the symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand with two molar equivalents of an organomagnesium halide of formula RMg(halide) or one molar equivalent of R2Mg, where R is (C1-C5)alkyl, CH2SiMe3, or benzyl, and the halide is Cl or Br, to produce a symmetric zirconium metallocene of structure (I), wherein each X is halogen, (C1-C5)alkyl, CH2SiMe3, or benzyl. One or more embodiments provide that X is (C1-C5)alkyl, CH2SiMe3, or benzyl. One or more embodiments provide that X is Cl or CH3. As used herein, all references to the Periodic Table of the Elements and its Groups, unless they refer to the previous IUPAC system designated by Roman numerals (which are also designated similarly), or unless otherwise stated, are references to the NEW NOTATION published in HAWLEY'S CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition, John Wiley & Sons, Inc., (1997) (reproduced with permission of IUPAC).

[0023] As used herein, "alkyl" includes straight-chain, branched-chain, and cyclic paraffinic groups that are deficient by one hydrogen. Thus, for example, CH ("methyl") and CHCH ("ethyl") are examples of alkyl.

[0024] As used herein, "alkenyl" includes straight-chain, branched-chain, and cyclic olefinic groups that are deficient by one hydrogen. Alkynyl groups include straight-chain, branched-chain, and cyclic acetylenic groups that are deficient by one hydrogen.

[0025] As used herein, "aryl" groups include phenyl, naphthyl, pyridyl, and other groups whose molecules have ring structures characteristic of benzene, naphthylene, phenanthrene, anthracene, etc. "Aryl" groups include C6-C 20 It is understood that the aromatic group may be an aryl group. For example, a C6H5 aromatic structure is "phenyl" and a C6H42 aromatic structure is "phenylene." An "arylalkyl" group is an alkyl group having an aryl group pendant therefrom. An "aralkyl" group is an alkyl group (C7-C 20 It is understood that the alkyl group may be an aryl group having one or more alkyl groups pendant therefrom.

[0026] As used herein, "alkylene" includes straight-chain, branched-chain, and cyclic hydrocarbon groups deficient by two hydrogens. Thus, CH ("methylene") and CHCH ("ethylene") are examples of alkylene groups. Other groups deficient by two hydrogens include "arylene" and "alkenylene."

[0027] As used herein, the term "heteroatom" includes any atom selected from the group consisting of B, Al, Si, Ge, N, P, O, and S. A "heteroatom-containing group" is a hydrocarbon group containing a heteroatom, which in certain embodiments may contain one or more of the same or different heteroatoms, and from one to three heteroatoms. Non-limiting examples of heteroatom-containing groups include imine, amine, oxide, phosphine, ether, ketone, oxoazoline complex cyclic compound, oxazoline, and thioether groups (monoradical and diradical).

[0028] As used herein, the term "substituted" means that one or more hydrogen atoms in a parent structure are independently replaced by a substituent atom or group.

[0029] The symmetric zirconium metallocenes having an isobutylcyclopentadienyl ligand discussed herein can be utilized to prepare catalyst compositions. These compositions include the symmetric zirconium metallocenes having an isobutylcyclopentadienyl ligand discussed herein and an activator. One or more embodiments provide that the activator is an alkylaluminoxane, such as methylaluminoxane. As used herein, "activator" refers to any compound or combination of compounds, supported or unsupported, that can activate a complex or catalyst component, for example, by generating a cationic species of the catalyst component. For example, this can include abstraction of at least one leaving group, such as an "X" group described herein, from the metal center of a complex / catalyst component, for example, a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand of structure (I). The activator is sometimes referred to as a "cocatalyst." As used herein, "leaving group" refers to one or more chemical moieties that are attached to a metal atom and capable of abstraction by an activator, thus generating a species active for olefin polymerization. A variety of catalyst compositions, e.g., olefin polymerization catalyst compositions, are known in the art, and different known catalyst composition components may be utilized. Varying amounts of the catalyst composition components may be utilized for different applications.

[0030] The symmetric zirconium metallocenes having isobutylcyclopentadienyl ligands discussed herein can be utilized to produce spray-dried compositions. As used herein, "spray-dried composition" refers to a composition containing several components that has undergone a spray-drying process. Various spray-drying processes are known in the art and are suitable for forming the spray-dried compositions disclosed herein. One or more embodiments provide that the spray-dried composition comprises a trim composition.

[0031] In one or more embodiments, the spray-drying process may include atomizing a composition comprising a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand as discussed herein. Several other known components may also be utilized in the spray-drying process. For example, a spray or dispersion of droplets of the composition may be created using an atomizer, such as an atomizing nozzle or a centrifugal high-speed disk. The droplets of the composition may then be rapidly dried by contacting them with an inert drying gas. The inert drying gas may be any gas that is non-reactive under the conditions employed during atomization, such as nitrogen. The inert drying gas may contact the composition in an atomizer that continuously generates a droplet stream. Dried particles of the composition may be captured from the process in a separator, such as a cyclone, which may separate the formed solids from the gaseous mixture of the drying gas, solvent, and other volatile components.

[0032] The spray-dried composition may, for example, have the form of a free-flowing powder. After the spray-drying process, the spray-dried composition and certain known ingredients may be utilized to form a slurry. The spray-dried composition may be utilized with a diluent to form a slurry suitable for use in, for example, olefin polymerization. In one or more embodiments, the slurry may be combined with one or more additional catalysts or other known ingredients before being delivered to a polymerization reactor.

[0033] In one or more embodiments, the spray-dried composition may be formed by contacting spray-dried activator particles, such as spray-dried MAO, with a solution of a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand, as discussed herein. Such a solution may typically be prepared, for example, in an inert hydrocarbon solvent and is sometimes referred to as a trim solution. Such a spray-dried composition, consisting of contacting a trim solution of a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand with spray-dried activator particles, such as spray-dried MAO, may be prepared in situ in the feed line to the gas-phase polymerization reactor by contacting the trim solution with a slurry of spray-dried activator particles, typically in mineral oil. Alternatively, the spray-dried composition may be formed by contacting a slurry of spray-dried activator particles (e.g., a mineral oil slurry of spray-dried activator particles) with a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand, as discussed herein.

[0034] Various spray drying conditions may be utilized for different applications. For example, the spray drying process may utilize a drying temperature of 115 to 185°C. Other drying temperatures are possible, and the temperature may depend on the metallocene and activator particles. Various sizes of orifices in the atomizing nozzle employed during the spray drying process may be utilized to obtain different particle sizes. Alternatively, in other types of atomizers, such as disks, the rotation speed, disk size, and number / size of holes may be adjusted to obtain different particle sizes. One or more embodiments provide that a filler may be utilized in the spray drying process. Different amounts of additives may be utilized for various applications.

[0035] Catalyst compositions, such as the symmetric zirconium metallocenes with isobutylcyclopentadienyl ligands discussed herein, e.g., spray-dried zirconium metallocene compositions, may be utilized to produce polymers. For example, symmetric zirconium metallocenes with isobutylcyclopentadienyl ligands may be activated, i.e., prepared using an activator. One or more embodiments provide that the spray-dried composition includes an activator. As used herein, "activator" refers to any compound or combination of compounds, supported or unsupported, that can activate a complex or catalyst component, for example, by generating a cationic species of the catalyst component to provide the catalyst. Activators are sometimes referred to as "cocatalysts." Activators can include Lewis acids or non-coordinating ionic activators or ionizing activators, or any other compounds, including Lewis bases, aluminum alkyls, and / or conventional cocatalysts. Activators include methylaluminoxane (MAO) and modified methylaluminoxane (MMAO), among others. One or more embodiments provide that the activator is methylaluminoxane. Activation conditions are well known in the art. Known activation conditions can be utilized.

[0036] The molar ratio of the metal in the activator, e.g., aluminum, to zirconium in the symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand may be from 1500:1 to 0.5:1, from 300:1 to 1:1, or from 150:1 to 1:1. One or more embodiments provide that the molar ratio of activator to zirconium in the symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand is at least 75:1. One or more embodiments provide that the molar ratio of activator to zirconium in the symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand is at least 100:1. One or more embodiments provide that the molar ratio of activator to zirconium in the symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand is at least 150:1.

[0037] The symmetric zirconium metallocenes having an isobutylcyclopentadienyl ligand, as well as certain other components discussed herein, may be supported on the same or separate supports, or one or more components may be used in unsupported form. Using a support can be accomplished by any technique used in the art. One or more embodiments provide that a spray-drying process is utilized. For example, a symmetric metallocene having an isobutylcyclopentadienyl ligand in an inert solvent can be contacted with a supported or spray-dried activator (or a slurry thereof) to obtain a spray-dried metallocene catalyst composition. Alternatively, the supported symmetric zirconium metallocenes of the present disclosure, as well as certain other components, can be formed by drying a slurry of the components under vacuum or reduced pressure. The support may be functionalized. One or more embodiments provide that the spray-dried composition includes a support.

[0038] "Support", which may also be referred to as "carrier", refers to any support material, including porous support materials such as talc, inorganic oxides, and inorganic chlorides. Other support materials include resinous support materials, functionalized or crosslinked organic supports such as polystyrene, polystyrene divinylbenzene polyolefins, or polymeric compounds, zeolites, clays, or any other organic or inorganic support material, or mixtures thereof.

[0039] Support materials include inorganic oxides, including Group 2, 3, 4, 5, 13, or 14 metal oxides. Some preferred supports include silica, fumed silica, alumina, silica-alumina, and mixtures thereof. Other supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicates, zeolites, talc, clay, and the like. Combinations of these support materials, such as silica-chromium, silica-alumina, and silica-titania, can also be used. One or more embodiments provide that the support is silica. One or more embodiments provide that the support is hydrophobic fumed silica. One or more embodiments provide that the support is dehydrated silica. Additional support materials include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymer beads. Additional support materials may include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymer beads. An example of a support is fumed silica available under the trade name Cabosil™ TS-610 or other TS or TG series supports available from Cabot Corporation. Fumed silica is typically silica with particles 7 to 30 nanometers in size that have been treated with dimethylsilyl dichloride so that most of the surface hydroxyl groups are capped.

[0040] A symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand, e.g., a catalyst composition / spray-dried composition, described herein, can be contacted with an olefin under polymerization conditions to produce a polymer, e.g., a polyolefin polymer. The polymerization process can be a solution polymerization process, such as a suspension polymerization process, a slurry polymerization process, and / or a gas-phase polymerization process. The polymerization process can be used using known equipment and reaction conditions, e.g., known polymerization conditions. The polymerization process is not limited to any particular type of polymerization system. The polymer can be utilized in many articles, such as films, fibers, nonwoven and / or woven fabrics, extruded articles, and / or molded articles.

[0041] One or more embodiments provide that the polymer is produced using a gas-phase reactor system. For example, one or more embodiments provide that a single gas-phase reactor is utilized, as opposed to a series of reactors. In other words, the polymerization reaction occurs only in one reactor. For example, the polymer may be produced using a fluidized bed reactor. Gas-phase reactors are known, and known components may be utilized in a fluidized bed reactor.

[0042] As used herein, "olefin," which may be referred to as "alkene," refers to a linear, branched, or cyclic compound containing carbon and hydrogen and having at least one double bond. As used herein, when a polyolefin, polymer, and / or copolymer is referred to as comprising, e.g., produced from, an olefin, the olefin present in such a polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an ethylene content of 75% to 95% by weight, it is understood that the polymer units in the copolymer are derived from ethylene in the polymerization reaction(s), and the derived units are present in 75% to 95% by weight, based on the total weight of the polymer. Higher α-olefin refers to an α-olefin having three or more carbon atoms.

[0043] Polyolefins produced using the compositions discussed herein can be produced from olefin monomers such as ethylene (i.e., polyethylene) or propylene (i.e., polypropylene), among others provided herein, and the polyolefins are homopolymers produced solely from olefin monomers (e.g., 100% by weight ethylene or 100% by weight propylene). Alternatively, polyolefins produced using the compositions discussed herein can be polymers produced from olefin monomers such as ethylene, i.e., polyethylene, and linear or branched higher α-olefin monomers containing 3 to 20 carbon atoms. Examples of higher α-olefin monomers include, but are not limited to, propylene, butene, pentene, 1-hexene, and 1-octene. Examples of polyolefins include, among others, ethylene-based polymers having at least 50% by weight ethylene, such as ethylene-1-butene, ethylene-1-hexene, and ethylene-1-octene copolymers. One or more embodiments provide that the polymer can comprise 50 to 99.9 wt. % ethylene-derived units, based on the total weight of the polymer. All individual values and subranges between 50 and 99.9 wt. % are included, for example, the polymer can comprise from a lower limit of 50, 60, 70, 80, or 90 wt. % ethylene-derived units to an upper limit of 99.9, 99.7, 99.4, 99, 96, 93, 90, or 85 wt. % ethylene-derived units, based on the total weight of the polymer. The polymer can comprise 0.1 to 50 wt. % comonomer-derived units, based on the total weight of the polymer. One or more embodiments provide that ethylene is utilized as the monomer and hexene is utilized as the comonomer.

[0044] As noted above, polymers made with the compositions disclosed herein can be produced in a fluidized bed reactor. The fluidized bed reactor can have a reaction temperature of 10 to 130° C. All individual values and subranges between 10 and 130° C. are included, for example, the fluidized bed reactor can have a reaction temperature from a lower limit of 10, 20, 30, 40, 50, or 55° C. to an upper limit of 130, 120, 110, 100, 90, 80, 70, or 60° C.

[0045] The fluidized bed reactor can have an ethylene partial pressure of from 30 to 250 pounds per square inch (psi), including all individual values and subranges between 30 and 250, for example, the fluidized bed reactor can have an ethylene partial pressure from a lower limit of 30, 45, 60, 75, 85, 90, or 95 psi to an upper limit of 250, 240, 220, 200, 150, or 125 psi.

[0046] One or more embodiments provide that ethylene is utilized as the monomer and hexene is utilized as the comonomer. The fluidized bed reactor may have a comonomer to ethylene molar ratio, e.g., C6 / C2, of 0.0001 to 0.100. All individual values and subranges from 0.0001 to 0.100 are included, for example, the fluidized bed reactor may have a comonomer to ethylene molar ratio from a lower limit of 0.0001, 0.0005, 0.0007, 0.001, 0.0015, 0.002, 0.007, or 0.010 to an upper limit of 0.100, 0.080, or 0.050.

[0047] If hydrogen is utilized in the polymerization process, the fluidized bed reactor may have, for example, a hydrogen to ethylene molar ratio (H2 / C2) of 0.00001 to 0.90000. All individual values and subranges from 0.00001 to 0.90000 are included, for example, the fluidized bed reactor may have a H2 / C2 from a lower limit of 0.00001, 0.00005, or 0.00008 to an upper limit of 0.90000, 0.500000, 0.10000, 0.01500, 0.00700, or 0.00500. One or more embodiments provide that no hydrogen is utilized.

[0048] Many polymer properties may be determined using conventional compositional gel permeation chromatography. For example, weight-average molecular weight (Mw), number-average molecular weight (Mn), Z-average molecular weight (Mz), and Mw / Mn (PDI) were determined using a chromatographic system consisting of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160°C, and the column compartment was set to 150°C. The columns used were four Agilent "Mixed A" 30 cm, 20 micron linear mixed-bed columns. The chromatographic solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / minute.

[0049] Calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000 g / mol, arranged in six "cocktail" mixtures with at least one decade between individual molecular weights. Standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights above 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights below 1,000,000. The polystyrene standards were predissolved at 80°C with gentle agitation for 30 minutes, then cooled, and the room temperature solution was transferred to an autosampler dissolving oven at 160°C for 30 minutes to cool. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)). M ポリエチレン =A×(M ポリエチレン ) B (Formula 1) where M is the molecular weight, A has a value of 0.4061, and B is equal to 1.0.

[0050] A fifth order polynomial was used to fit each polyethylene equivalent calibration point.

[0051] A total plate count for the GPC column set was performed using decane as a blank sample introduced via a micropump controlled using a PolymerChar GPC-IR system. The plate count for the chromatography system should exceed 18,000 for four Agilent "Mixed A" 30 cm 20 micron linear mixed-bed columns.

[0052] Samples were prepared in a semi-automated fashion using PolymerChar's "Instrument Control" software, with a target sample weight of 2 mg / ml, and solvent (containing 200 ppm BHT) was added via a PolymerChar high-temperature autosampler to a pre-nitrogen-sparged, septum-capped vial. Samples were dissolved at 160°C for 2 hours under "slow" shaking.

[0053] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation was based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 2-4 using PolymerChar's GPCONE software, baseline-subtracted IR chromatograms at each equally spaced data collection point (i), and polyethylene equivalent molecular weights obtained from a narrow standard calibration curve for point (i) of Equation 1.

[0054] [ka]

[0055] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to determine the relative position of each decane peak (RV) in the sample. (FM試料) ) and narrow reference material calibration (RV (FM較正済み) The pump flow rate (flow rate) for each sample was determined by matching the RV with that of the decane peak in the (見かけ) Any change in the time of the decane marker peak was then linearly corrected for the flow rate (flow rate (有効) ) is assumed to be related to a linear shift in the apparent flow rate. After calibrating the system based on the flow rate marker peaks, the effective flow rate (for a narrow standard calibration) is calculated as per Equation 5. Processing of the flow rate marker peaks was performed via PolymerChar's GPCOne™ software. An acceptable flow rate correction is such that the effective flow rate should be within ±0.5% of the apparent flow rate. Flow rate (effective) = Flow rate (nominal) * (RV(FM calibrated) / RV(FM sample)) (Equation 5)

[0056] IR5 GPC Octene Composition Calibration. Quantitative calibration of the IR5 detector is based on a narrow SCB distribution ranging from homopolymer (0 SCB / 1000 total carbons) to approximately 40 SCB / 1000 total carbons (where total C = carbons in the main chain + carbons in the branches) and known comonomer content ( 13 A study was conducted using at least 10 ethylene-based polymer standards (octene as a comonomer) produced by single-site metallocene catalysis from a single reactor (polyethylene homopolymer and ethylene / octene copolymer) in a solution process (measured by C NMR Method, Qiu et al., Anal. Chem. 2009, 81, 8585-8589). Each standard had a weight average molecular weight (Mw) of 36,000 g / mol to 126,000 g / mol as measured by GPC. Each standard had a molecular weight distribution (Mw / Mn) of 2.0 to 2.5. The polymer properties of the SCB standards are shown in Table A.

[0057] [Table 1]

[0058] The "IR5 area ratio" (or "IR5 area ratio") of the "baseline-subtracted area response of the IR5 methyl channel sensor" to the "baseline-subtracted area response of the IR5 measurement channel sensor" メチルチャネル面積 / IR5 測定チャネル面積 ")" (Standard filters and filter wheel supplied by PolymerChar: Part Number IR5_FWM01 included as part of the GPC-IR instrument) were calculated for each of the "copolymer" standards. A linear fit of wt% comonomer frequency versus "IR5 area ratio" was constructed in the form of Equation 6 below. Wt% Comonomer = A0 + [A1 × (IR5 メチルチャネル面積 / IR5 測定チャネル面積 )] (Equation 6) where A0 is the "wt% comonomer" at an "IR5 area ratio" of zero, and A1 is the slope of "wt% comonomer" vs. "IR5 area ratio," representing the increase in wt% comonomer as a function of "IR5 area ratio." The IR5 area ratio is equal to the IR5 height ratio for the narrow PDI and narrow SCBD standard material.

[0059] The comonomer distribution or short-chain branching distribution in ethylene / α-olefin copolymers can be characterized as either normal (also referred to as having a Ziegler-Natta distribution), inverted, or flat. Several reported methods are used to quantify broad orthogonal composition distributions (BOCDs). Herein, a simple line fit is used so that the normal or inverted nature of the comonomer distribution can be quantified by the molecular weight comonomer distribution index (MWCDI), which is the slope of the linear regression of the comonomer distribution obtained from compositional GPC measurements, where the x-axis is Log(MW) and the y-axis is the weight percent comonomer. Figure 1 shows the data plots used to determine the MWCDI for Example 1-2 (MWCDI = 1.41) and Comparative Example A-2 (MWCDI = 0.52), as shown in Table 1 in the Examples section of this application. An inverted comonomer distribution is defined when the MWCDI is greater than 0, and a normal comonomer distribution is defined when the MWCDI is less than 0. When MWCDI=0, the comonomer distribution is said to be flat. In addition, MWCDI quantifies the magnitude of the comonomer distribution. When comparing two polymers with MWCDI>0, the polymer with the larger MWCDI value is defined as having a larger, i.e., increased, BOCD. In other words, the polymer with the larger MWCDI value has a larger inverse comonomer distribution. For example, as reported in Table 1, Example 1-2 has an increased BOCD compared to Comparative Example A-2. A polymer with a relatively large MWCDI, i.e., BOCD, may provide improved physical properties, such as improved film properties, compared to a polymer with a relatively small MWCDI.

[0060] Polymers made with the compositions disclosed herein can have an MWCDI of 0.10 to 10.00, including all individual values and subranges between 0.10 and 10.00, for example, polymers can have a MWCDI from a lower limit of 0.10, 0.50, or 1.00 to an upper limit of 10.00, 9.00, 8.00, 8.50, or 8.35.

[0061] The polymers produced with the compositions disclosed herein have a viscosity of 0.8700 to 0.9700 g / cm 3 It may have a density of 0.8700 to 0.9700 g / cm 3 All individual values and subranges are included, for example, a polymer may have a viscosity of 0.8700, 0.9000, 0.9100, 0.9150, 0.9200, or 0.9250 g / cm 3 from the lower limit of 0.9700, 0.9600, 0.9500, 0.9450, 0.9350, or 0.9300 g / cm 3 The density may be determined according to ASTM D792.

[0062] Polymers produced with the compositions disclosed herein can have a weight average molecular weight (Mw) of 5,000 to 750,000 g / mol. All individual values and subranges between 5,000 and 750,000 g / mol are included. For example, the polymers can have Mw from lower limits of 5,000, 10,000, or 15,000 g / mol to upper limits of 750,000, 500,000, or 200,000 g / mol. Mw can be determined by gel permeation chromatography (GPC), as known in the art. GPC is discussed herein.

[0063] Polymers produced with the compositions disclosed herein can have a number average molecular weight (Mn) of 3,000 to 300,000 g / mol. All individual values and subranges between 3,000 and 300,000 g / mol are included. For example, the polymers can have Mn values from lower limits of 3,000, 5,000, or 10,000 g / mol to upper limits of 300,000, 250,000, or 200,000 g / mol. Mn can be determined by GPC, as described below.

[0064] Polymers produced with the compositions disclosed herein can have a Z-average molecular weight (Mz) of 20,000 to 2,000,000 g / mol. All individual values and subranges between 20,000 and 2,000,000 g / mol are included. For example, the polymers can have an Mz from lower limits of 20,000, 25,000, or 30,000 g / mol to upper limits of 2,000,000, 1,000,000, 500,000, or 200,000 g / mol. Mz can be determined by GPC.

[0065] Polymers produced with the compositions disclosed herein can have a weight average molecular weight to number average molecular weight ratio (Mw / Mn) of 1.00 to 6.00, including all individual values and subranges between 1.00 and 6.00, for example, polymers can have Mw / Mn from lower limits of 1.00, 1.50, 2.00, or 2.10, to upper limits of 6.00, 5.50, or 4.50.

[0066] Some aspects of the present disclosure are provided below.

[0067] Embodiment 1 is a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand represented by structure (I):

[0068] [ka] Each X is independently a leaving group, providing a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand.

[0069] Embodiment 2 provides a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand of embodiment 1, wherein each X is independently a leaving group selected from halogen, (C1-C5) alkyl, CH2SiMe3, and benzyl.

[0070] Aspect 3 provides having the isobutylcyclopentadienyl ligand of Aspects 2 or 3, wherein each X is Cl, or each X is CH3, as represented by structures (II) and (III).

[0071] [ka]

[0072] Embodiment 4 is a method for synthesizing a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand according to any one of embodiments 1-3, comprising: contacting the zirconium complex with an alkali metal complex, wherein the alkali metal complex is represented by the following structure:

[0073] [ka] wherein M' is lithium, sodium, or potassium; R 1 is an isobutyl group and the zirconium complex is zirconium tetrachloride.

[0074] Embodiment 5 provides the process of embodiment 4, comprising contacting a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand with two molar equivalents of an organomagnesium halide of formula RMg(halide) or one molar equivalent of R2Mg, where R is (C1-C5) alkyl, CH2SiMe3, or benzyl, and the halide is Cl or Br, to produce a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand of structure (I), wherein each X is (C1-C5) alkyl, CH2SiMe3, or benzyl.

[0075] Embodiment 6 provides a metallocene catalyst composition comprising the symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand of any one of Embodiments 1-3, or the symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand produced by the method of Embodiment 4 or Embodiment 5, and an activator (e.g., an alkylaluminoxane such as methylaluminoxane).

[0076] Embodiment 7 provides the metallocene catalyst composition of embodiment 6, further comprising a support (e.g., silica, such as hydrophobic fumed silica or dehydrated silica).

[0077] Embodiment 8 provides the metallocene catalyst composition of embodiment 7, wherein the composition is a spray-dried metallocene catalyst composition.

[0078] Embodiment 9 provides a method of making the metallocene catalyst composition of any one of Embodiments 6-8, comprising contacting a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand with an activator rather than a support to obtain the unsupported metallocene catalyst composition; or contacting a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand with an activator and a support to obtain the supported metallocene catalyst composition; or contacting a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand with an activator and a support in an inert solvent; or contacting a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand with an activator and a support in an inert solvent to obtain a suspension thereof and spray drying the suspension to obtain the spray-dried metallocene catalyst composition; or contacting a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand with a supported or spray-dried activator (or a slurry thereof) in an inert solvent to obtain the spray-dried metallocene catalyst composition.

[0079] Embodiment 10 is a method of producing a polyolefin polymer, comprising polymerizing at least one olefin monomer with the metallocene catalyst composition of any one of embodiments 6-8, or any of the metallocene catalyst compositions produced by the method of embodiment 9, to produce a polyolefin polymer, preferably wherein the at least one olefin monomer is ethylene and, optionally, propene and (C4-C 20 and a comonomer selected from the group consisting of: α-olefins.

[0080] Example 11 provides the method of example 10, wherein the at least one olefin monomer comprises ethylene and a comonomer, and the polyolefin polymer has a Molecular Weight Comonomer Distribution Index (MWCDI) of 0.10 to 10.00, as measured by the MWCDI test method described herein, and preferably the comonomer is selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

[0081] Aspect 12 provides a polyolefin polymer produced by the method of any one of aspects 10-11. [Example]

[0082] 5-(2-methylpropylidene)cyclopenta-1,3-diene, which can be represented by the following formula:

[0083] [ka] The synthesis was carried out as follows: In a glovebox, pyrrolidine (1.45 g, 10 mol%) was added to a glass vessel containing a solution of isobutyraldehyde (14.6 g, 203 mmol) and cyclopentadiene (13.4 g, 203 mmol) in MeOH-HO (200 mL 4 / 1). The contents of the vessel were transferred to an ice-cold mixture of brine solution and 10 mol% AcOH in a narrow graduated cylinder. The organic phase was isolated and dried over molecular sieves. The product (5-(2-methylpropylidene)cyclopenta-1,3-diene) was filtered to give a bright yellow oil, which was subsequently used without further purification (16.0 g, 65%). 1 H NMR(400MHz, CDCl3)δ:6.54(tdd,J=5.4,3.8,2.5Hz,2H),6.51-6.44(m,1H),6.29-6.17(m,2H),3.02(dp,J=10.0,6.6Hz,1H),1.15(d,J=6.6Hz,6H). 13 C NMR(101MHz, CDCl3)δ:149.88,143.69,133.08,130.87,126.06,119.36,30.58,23.24.

[0084] Iso-butylcyclopentadienyllithium, which can be represented by the formula:

[0085] [ka] It was synthesized as follows.

[0086] Et2O (250 mL) was added to the vessel. 5-(2-methylpropylidene)cyclopenta-1,3-diene (16.0 g, 133 mmol) was added to the contents of the vessel with stirring. LiAlH4 (33 mL, 4 M Et2O solution) was added dropwise to the contents of the vessel with stirring. Bubbling was observed. A white solid precipitated during the addition, and the yellow color gradually disappeared as the addition of LiAlH4 continued. The addition was stopped when the solution turned a very faint yellow color. The product, iso-butylcyclopentadienyllithium, observed to be a white solid, was collected by filtration, rinsed with Et2O, and dried under vacuum (13.7 g, 80%).

[0087] Example 1-1, as previously described, is a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand represented by structure (I), and was prepared as follows.

[0088] Iso-butylcyclopentadienyllithium (0.150 g, 17.7 mmol) and zirconium tetrachloride (0.136 g, 0.585 mmol) were added to the vessel along with THF and stirred at about 20° C. for about 12 hours. The contents of the vessel were then concentrated to give a yellowish residue. The residue was extracted with dichloromethane and then filtered. The resulting solution was placed under vacuum to give Example 1-1 (0.207 g, 87%). 1 H NMR (400MHz, C6D6): δ5.91(t,J=2.7Hz,1H),5.73(t,J=2.7Hz,1H),2.55(d,J=7.0Hz,1H),1.63(dp,J=13.5,6.8Hz,1H),0.79(d,J=6.6Hz,3H). 13 C NMR (101MHz, C6D6): δ132.75,117.48,111.48,39.57,30.17,22.06.

[0089] Spray-dried composition Example 1-2 was prepared as follows: In a nitrogen-purged glovebox, hydrophobic fumed silica (CABOSIL TS-610, 1.33 grams) and toluene (37.5 grams) were added to a container and mixed, followed by the addition of a 10 wt% solution of methylaluminoxane (MAO) in toluene (11 grams). The contents of the container were stirred for approximately 15 hours. Example 1-1 (0.040 grams) was then added to the container, and the contents of the container were stirred for approximately 30 minutes. The contents of the container were then spray-dried using a Buchi Mini Spray Dryer B-290 (set temperature 140°C, reaction temperature 100°C, pump speed 150 rpm) to provide Example 1-2.

[0090] Comparative Example A-1, a zirconium metallocene having two n-butylcyclopentadienyl ligands (bis-(n-butylcyclopentadienyl)zirconium dichloride), was obtained commercially from Boulder Scientific Company.

[0091] A spray-dried composition, Comparative Example A-2, was prepared as follows: In a nitrogen-purged glovebox, hydrophobic fumed silica (CABOSIL TS-610, 1.33 grams) and toluene (37.5 grams) were added to a container and mixed, followed by the addition of a 10 wt % solution of methylaluminoxane (MAO) in toluene (11 grams). The contents of the container were stirred for approximately 15 hours. Comparative Example A-1 (0.050 grams) was then added to the container, and the contents of the container were stirred for approximately 30 minutes. The contents of the container were then spray-dried using a Buchi Mini Spray Dryer B-290 (set temperature 140°C, reaction temperature 100°C, aspirator 95, pump speed 150 rpm) to provide Comparative Example A-2.

[0092] Polymerizations were conducted as follows. For each polymerization, dry NaCl (200 g) was charged to a laboratory-scale gas-phase polymerization reactor (a 2-liter stainless steel autoclave equipped with a variable-speed mechanical stirrer) and heated to 100°C under a nitrogen flow for 1 hour. The reactor was then purged with nitrogen, silica-supported methylaluminoxane was added to the reactor as a scavenger, the reactor temperature was adjusted to approximately the desired temperature, the reactor was sealed, and the reactor contents were stirred. The reactor was precharged with hydrogen, ethylene, and 1-hexene to the desired pressure. Once steady state was reached, the catalyst was charged to the reactor (at the temperature indicated below) to initiate the polymerization. The reactor temperature was maintained at the desired temperature for 60 minutes of polymerization. The hydrogen, C6 / C2 ratio, and ethylene pressure were maintained constant. At the end of the 60-minute polymerization, the reactor was cooled, vented, and opened. The resulting mixture was washed with water and methanol and dried. The polymerization conditions are listed in Tables 1–3.

[0093] Several properties were measured for the polymers produced in Examples 1-2 and Comparative Example A-2. The results are shown in Table 1. Catalyst productivity (grams of polymer / grams of catalyst-hours) was determined as the ratio of polymer produced to the amount of catalyst added to the reactor. Melt index (I2) was determined according to ASTM D1238 (190°C, 2.16 kg), melt index (I5) was determined according to ASTM D1238 (190°C, 5 kg), and melt index (I 21 ) was determined according to ASTM D1238 (190°C, 21.6 kg). Melting temperature was determined using differential scanning calorimetry according to ASTM D 3418-08, using a scan rate of 10°C / min on a 10 mg sample, and T using a second heating cycle. m were determined. Mw, Mn, Mz, and Mw / Mn were determined by GPC. Molecular weight comonomer distribution index (MWCDI) was determined as discussed herein.

[0094] [Table 2]

[0095] [Table 3]

[0096] [Table 4]

[0097] The data in Tables 1-3 show that the polymer produced in Example 1-2 had an improved, i.e., higher, molecular weight comonomer distribution index (MWCDI) compared to the polymer produced in Comparative Example A-2.

[0098] In addition, the data in Tables 1-3 show that the polymers produced in Examples 1-2 had improved, i.e., greater, comonomer incorporation (C6 wt %) compared to the polymers produced in Comparative Example A-2.

[0099] 1 shows the data plots used to determine the MWCDI for Example 1-2 (MWCDI=1.41) and Comparative Example A-2 (MWCDI=0.52), as shown in Table 1. Data plot 102 corresponds to the determination of the MWCDI for Example 1-2. Data plot 104 corresponds to the determination of the MWCDI for Example A-2.

Claims

1. A symmetrical zirconium metallocene having an isobutylcyclopentadienyl ligand represented by structure (I): 【Chemical 1】 A symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand, wherein each X is independently a leaving group.

2. Each X is independently a halogen, (C １ ~C ５ ) alkyl, CH ２ SiMe ３ 2. The symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand according to claim 1, wherein the leaving group is selected from the group consisting of cyclopentadienyl, ...

3. Each X is Cl, or each X is a CH group represented by structures (II) and (III) ３ 4. A symmetrical zirconium metallocene having an isobutylcyclopentadienyl ligand according to claim 2 or 3, wherein: 【Chemistry 2】

4. A method for synthesizing a symmetrical zirconium metallocene having an isobutylcyclopentadienyl ligand according to any one of claims 1 to 3, comprising the steps of: contacting a zirconium complex with an alkali metal complex, wherein the alkali metal complex is represented by the following structure: 【Chemistry 3】 wherein M′ is lithium, sodium, or potassium; R １ is an isobutyl group and the zirconium complex is zirconium tetrachloride.

5. The symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand is reacted with two molar equivalents of an organomagnesium halide of formula RMg(halide) or one molar equivalent of R ２ Mg (wherein R is (C １ ~C ５ ) alkyl, CH ２ SiMe ３ or benzyl, and the halide is Cl or Br), to prepare a symmetrical hafnium metallocene having the isobutylcyclopentadienyl ligand of structure (I), wherein each X is (C １ ~C ５ ) alkyl, CH ２ SiMe ３ or benzyl.

6. 1. A metallocene catalyst composition comprising: A metallocene catalyst composition comprising a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand according to any one of claims 1 to 3, or a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand produced by the method of claim 4 or claim 5, and an activator.

7. The metallocene catalyst composition of claim 6 further comprising a support.

8. 8. The metallocene catalyst composition of claim 7, wherein the composition is a spray-dried metallocene catalyst composition.

9. A method for producing the metallocene catalyst composition of any one of claims 6 to 8, comprising contacting the symmetric zirconium metallocene having isobutylcyclopentadienyl ligands with the activator but not with the support to obtain the metallocene catalyst composition without a support, or contacting the symmetric zirconium metallocene having isobutylcyclopentadienyl ligands with the activator and the support to obtain the metallocene catalyst composition with the support, or contacting the symmetric zirconium metallocene having isobutylcyclopentadienyl ligands in an inert solvent. or contacting the symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand with the activator and the support in an inert solvent to obtain a suspension thereof and spray drying the suspension to obtain the spray-dried metallocene catalyst composition; or contacting a symmetric zirconium metallocene having an isobutylcyclopentadienyl ligand with the activator and the support in an inert solvent to obtain a suspension thereof and spray drying the suspension to obtain the spray-dried metallocene catalyst composition.

10. 1. A method for producing a polyolefin polymer, comprising:

10. The method of claim 9, further comprising polymerizing at least one olefin monomer with either the metallocene catalyst composition of any one of claims 6 to 8 or the metallocene catalyst composition produced by the method of claim 9 to produce the polyolefin polymer, wherein preferably the at least one olefin monomer is ethylene and, optionally, propene and (C ４ ~C ２０ ) a comonomer selected from the group consisting of α-olefins.

11. 11. The method of claim 10, wherein the at least one olefin monomer comprises ethylene and said comonomer, and the polyolefin polymer has a Molecular Weight Comonomer Distribution Index (MWCDI) of 0.10 to 10.00 as measured by the MWCDI Test Method described herein, and preferably said comonomer is selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

12. A polyolefin polymer produced by the method of any one of claims 10 to 11.

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