Asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand

Abstract

Embodiments of the present disclosure relate to an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand, a composition containing an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand, and a method of using a composition containing an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand.

Description

Technical Field

[0001] Embodiments of the present disclosure relate to an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand, a catalyst composition comprising the asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand, a method for producing the same and a method for using the same, and a polyolefin produced thereby.

Background Art

[0002] Metallocenes can be used in various applications including polymerization catalysts. Polymers can be utilized in many articles including, in particular, 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] An asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand represented by structure (I),

[0005]

Chem.

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

[0007] A method for producing an asymmetric metallocene catalyst composition, the method comprising contacting an asymmetric 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 an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand catalyst composition to produce a polyolefin polymer.

Mode for Carrying Out the Invention

[0009] Asymmetric zirconium metallocenes having an isobutylcyclopentadienyl ligand are discussed herein. Advantageously, these asymmetric zirconium metallocenes having an isobutylcyclopentadienyl ligand can be utilized, for example, to produce catalyst compositions. These catalyst compositions can be utilized, for example, to produce polymers having an inverse comonomer distribution, such as a molecular weight comonomer distribution index (MWCDI) > 0, as further discussed herein. These polymers are particularly desirable for many applications, including films. Thus, it is advantageous to provide an inverse comonomer distribution. Such polymers are advantageous for many applications. In addition, the polymers can have an inverse short chain branch distribution (rSCBD), also referred to as a broad orthogonal composition distribution (BOCD), which is surprising for Zr catalysts. In addition, these catalyst compositions can be utilized to produce polymers having improved, i.e., greater comonomer incorporation (C6 wt %), compared to polymers produced from other metallocenes.

[0010] Asymmetric zirconium metallocenes having isobutylcyclopentadienyl ligands can also be used to provide polymers having an improved inverse short chain branching distribution, as discussed herein. A defining characteristic of polymers such as poly(ethylene-co-1-alkene) resins is the short chain branching distribution (SCBD), or comonomer distribution. For improved product performance in many applications, it is desirable to have an inverse SCBD or inverse comonomer distribution where the weight percent (wt%) of comonomer in the polymer increases as the molecular weight (MW) of the polymer chains increases. This is also referred to as a polymer having a broad orthogonal composition distribution (BOCD). Such distributions are typically obtained using a dual reactor configuration and single or dual catalyst processes. In a dual reactor process, a single catalyst can be used to produce a high MW low density component (having a higher comonomer wt%) and a low MW high density (lower comonomer wt%) component in separate reactors via independent process control within the two reactors. The result is a bimodal resin having an inverse 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 having an inverse SCBD.

[0011] A more desirable way to obtain polymers having an inverse SCBD is to use a single catalyst that can produce such BOCD resins in a single reactor. The asymmetric zirconium metallocenes having isobutylcyclopentadienyl ligands of the present disclosure, as discussed herein, have the ability to produce polymers in a single reactor having improved BOCD resins, particularly polymers having a measurable greater tendency for the comonomer to chain onto the higher MW fractions and maintaining significant BOCD characteristics over a wide range of process conditions. In addition, there is a need in the industry for low melt index resins having a broad molecular weight distribution and high BOCD compositions for films and other applications. Without being bound by theory, the iso-butyl group of the asymmetric zirconium metallocenes having isobutylcyclopentadienyl ligands of the present disclosure is a primary C(sp 3)-Increase the number of -H bonds, thereby increasing the frequency of this reaction, enhancing the tendency towards multi-site nature of the asymmetric zirconium metallocene catalyst having an isobutylcyclopentadienyl ligand, and generating a polymer having BOCD.

[0012] The asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand can be represented by structure (I),

[0013] [Chemical formula] Each X is, independently, a leaving group. As shown in structure (I), the upper cyclopentadienyl ring is substituted with an isobutyl group, also called a 2-methylpropyl group, having a monovalent structure -CH2CH(CH3)2, and the lower cyclopentadienyl ring is unsubstituted.

[0014] 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 alkyl and halogen. One or more embodiments provide that X is Cl. One or more embodiments provide that X is methyl. One or more embodiments provide that X is selected from halogen, (C1-C5)alkyl, CH2SiMe3, and benzyl.

[0015] Examples of X include halide 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-C 12)Heteroatom-containing hydrocarbons and their substituted derivatives are included. One or more embodiments include hydrides, halogen ions, (C1-C6) alkyl, (C2-C6) alkenyl, (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 hydrides, chlorides, fluorides, 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 chlorides, fluorides, (C1-C6) alkyl, (C2-C6) alkenyl, (C7-C 18 ) alkylaryl, halogenated (C1-C6) alkyl, halogenated (C2-C6) alkenyl, and halogenated (C7-C 18)It includes 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).

[0016] Other non-limiting examples of the X group include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon groups having 1 to 20 carbon atoms, fluorinated hydrocarbon groups such as -C6F5 (pentafluorophenyl), fluorinated alkyl carboxylates such as CF3C(O)O-, hydrides, halogen ions, and combinations thereof. Other examples of the X ligand include, in particular, alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, and dimethylphosphide groups. In one embodiment, two or more Xs form part of a fused ring or ring system. In one or more embodiments, X is a chloride ion, bromide ion, (C1-C 10 )alkyl, (C2-C 12 )alkenyl, carboxylate, acetylacetonate, and alkoxide, and can be a leaving group selected from the group consisting of. In one or more embodiments, X is methyl.

[0017] The asymmetric zirconium metallocene with isobutylcyclopentadienyl ligand discussed herein can be produced by contacting a Zr complex with an alkali metal complex to produce an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand. As an example, the alkali metal complex can be a lithium complex such as isobutylcyclopentadienyllithium. The asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand discussed herein can be produced, for example, by a process using conventional solvents, reaction conditions, reaction times, and isolation procedures utilized to produce known metallocenes.

[0018] The alkali metal complex can be represented by the following structure:

[0019] [Chemical formula] In the formula, M’ is lithium, sodium, or potassium; R 1 is H.

[0020] One or more embodiments provide that the zirconium complex can be represented by one of the following structures:

[0021] [Chemical formula] In the formula, R 1 is H.

[0022] One or more embodiments provide, for example, a method for producing an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand in which each X is Cl, by contacting an asymmetric metallocene with 2 molar equivalents of an organomagnesium halide of the formula RMg(halide) or 1 molar equivalent of the formula R2Mg (wherein R is (C1-C5) alkyl, CH2SiMe3, or benzyl, and the halide is Cl or Br), to produce an asymmetric metallocene of structure (I), and each X is halogen, (C1-C5) alkyl, CH2SiMe3, or benzyl. One or more embodiments provide that X is (C1-C5) alkyl, CH2SiMe3, or benzyl.

[0023] As used herein, all references to the Periodic Table and its groups refer to the NEW NOTATION published in HAWLEY’S CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition, John Wiley & Sons, Inc., (1997) (reproduced with permission from IUPAC), unless otherwise indicated or specifically stated, in which case they refer to the previous IUPAC system denoted by Roman numerals (which is also shown in the same way).

[0024] As used herein, "alkyl" includes straight-chain, branched-chain, and cyclic paraffin groups lacking one hydrogen. Thus, for example, CH3 ("methyl") and CH2CH3 ("ethyl") are examples of alkyls.

[0025] As used herein, "alkenyl" includes straight-chain, branched-chain, and cyclic olefin groups lacking one hydrogen. Alkynyl groups include straight-chain, branched-chain, and cyclic acetylene groups lacking one hydrogen group.

[0026] As used herein, "aryl" groups include phenyl, naphthyl, pyridyl, and other groups having a ring structure characteristic of benzene, naphthylene, phenanthrene, anthracene, etc. An "aryl" group can be a C6 - C 20 It is understood that it can be an aryl group. For example, the C6H5 aromatic structure is "phenyl", and the C6H42 aromatic structure is "phenylene". An "arylalkyl" group is an alkyl group having an aryl group hanging therefrom. An "aralkyl" group can be a (C7 - C 20 ) aralkyl group as understood. "Alkylaryl" is an aryl group having one or more alkyl groups hanging therefrom.

[0027] As used herein, "alkylene" includes linear, branched, and cyclic hydrocarbon groups lacking two hydrogens. Thus, CH2 ("methylene") and CH2CH2 ("ethylene") are examples of alkylene groups. Other groups lacking two hydrogens include "arylene" and "alkenylene".

[0028] 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 and, in certain embodiments, may contain one or more of the same or different heteroatoms and from 1 to 3 heteroatoms. Non-limiting examples of heteroatom-containing groups include imine, amine, oxide, phosphine, ether, ketone, oxazoline complex cyclic compounds, oxazoline, and thioether groups (monoradicals and diradicals).

[0029] As used herein, the term "substituted" means that one or more hydrogen atoms in the parent structure have been independently replaced by a substituent atom or group.

[0030] The asymmetric zirconium metallocenes having isobutylcyclopentadienyl ligands discussed herein can be utilized to produce catalyst compositions. These asymmetric metallocene compositions include an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand 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 involve the extraction of at least one leaving group from the metal center of the complex / catalyst component, e.g., the "X" group described herein, of an asymmetric metallocene 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 bonded to a metal atom and can be extracted by an activator, and thus can generate a species that is active towards olefin polymerization. Various catalyst compositions, e.g., olefin polymerization catalyst compositions, are known in the art and different known catalyst composition components may be utilized. Various amounts of the catalyst composition components can be utilized for different applications.

[0031] The asymmetric 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 have 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 includes a trim composition.

[0032] In one or more embodiments, the spray drying process may include atomizing a composition comprising an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand. Several other known components may be utilized in the spray drying process. For example, an atomizer such as an atomizing nozzle or a centrifugal high-speed disk may be used to create a spray or dispersion of droplets of the composition. Next, the droplets of the composition may 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 with an atomizer that continuously generates a stream of droplets. The dried particles of the composition may be captured from the process in a separator such as a cyclone that can separate solids formed from a gaseous mixture of the drying gas, solvent, and other volatile components.

[0033] The spray-dried composition may have, for example, the form of a free-flowing powder. After the spray drying process, a slurry may be formed using the spray-dried composition and several known components. The spray-dried composition may be utilized with a diluent to form, for example, a slurry suitable for use in olefin polymerization. In one or more embodiments, the slurry may be combined with one or more additional catalysts or other known components before being delivered to the polymerization reactor.

[0034] 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 an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand. Such solutions can typically be prepared, for example, in an inert hydrocarbon solvent and may also be referred to as trim solutions. Such a spray-dried composition, which consists of contacting a trim solution of an asymmetric metallocene with spray-dried activator particles, such as spray-dried MAO, may be produced in situ in a feed line leading to a gas-phase polymerization reactor by contacting the trim solution with a slurry of spray-dried activator particles, typically a slurry 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 an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand as discussed herein.

[0035] Various spray-drying conditions may be utilized for different applications. For example, the spray-drying process may use a drying temperature of 115 - 185 °C. Other drying temperatures are possible and the temperature may depend on the metallocene and activator particles. Different particle sizes may be obtained using various sized orifices of the atomizing nozzle employed during the spray-drying process. Alternatively, with other types of atomizers, such as disks, different particle sizes may be obtained by adjusting the rotational speed, disk size, and number / size of the holes. One or more embodiments provide that a filler may be utilized in the spray-drying process. Different amounts of additives can be utilized for various applications.

[0036] Asymmetric zirconium metallocenes having isobutylcyclopentadienyl ligands discussed herein, such as spray-dried asymmetric metallocene compositions and the like, may be utilized to produce polymers. For example, the asymmetric metallocene may be activated, i.e., an asymmetric metallocene catalyst may be produced using an activator. One or more embodiments provide that the spray-dried composition contains an activator. As used herein, an "activator" refers to any supported or unsupported compound or combination of compounds that can activate a complex or catalyst component, for example, by generating a cationic species of the catalyst component to provide a catalyst. An activator is sometimes referred to as a "cocatalyst". The activator can include a Lewis acid or a non-coordinating ionic activator or an ionizing activator, or any other compound including a Lewis base, an aluminum alkyl, and / or a conventional type cocatalyst. Particularly, methylaluminoxane (MAO) and modified methylaluminoxane (MMAO) are mentioned as activators. One or more embodiments provide that the activator is methylaluminoxane. The activation conditions are well-known in the art. Known activation conditions can be utilized.

[0037] The molar ratio of the metal in the activator, such as aluminum, to zirconium in the asymmetric 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 the activator to Zr in the asymmetric metallocene is at least 75:1. One or more embodiments provide that the molar ratio of the activator to Zr in the asymmetric metallocene is at least 100:1. One or more embodiments provide that the molar ratio of the activator to Zr in the asymmetric metallocene is at least 150:1.

[0038] The asymmetric zirconium metallocenes having isobutylcyclopentadienyl ligands discussed herein, as well as several other components, can be supported on the same or separate carriers or can be used in a form in which one or more components are not supported. The use of a carrier can be achieved by any technique used in the art. One or more embodiments provide that a spray drying process is utilized. For example, an asymmetric 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 asymmetric zirconium metallocenes having isobutylcyclopentadienyl ligands of the present disclosure, as well as several other components, can be formed by drying a slurry of the components under vacuum or reduced pressure. The carrier may be functionalized. One or more embodiments provide that the spray dried composition includes a carrier.

[0039] The "carrier", which may also be referred to as a "support", refers to any carrier material including a porous carrier material such as, for example, talc, inorganic oxides, and inorganic chlorides. Other carrier materials include resin carrier materials such as functionalized or crosslinked organic carriers such as polystyrene, polystyrene divinylbenzene polyolefins, or polymeric compounds, zeolites, clays, or any other organic or inorganic carrier material, or mixtures thereof.

[0040] Examples of the carrier material include inorganic oxides containing metal oxides of Groups 2, 3, 4, 5, 13, or 14. Some preferred carriers include silica, fumed silica, alumina, silica-alumina, and mixtures thereof. Some other carriers include magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate, zeolite, talc, clay, and the like. Also, combinations of these carrier materials, such as silica-chromium, silica-alumina, silica-titania, and the like can be used. One or more embodiments provide that the carrier is hydrophobic fumed silica. Further examples of carrier materials include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymer beads. Further examples of carrier materials may include porous acrylic polymers, nanocomposites, aerogels, spherulites, and polymer beads. An example of the carrier is fumed silica available under the trade name Cabosil™ TS-610, or other TS or TG series carriers available from Cabot Corporation. Fumed silica is typically silica having particles sized 7 to 30 nanometers that have been treated with dimethylsilyl dichloride such that most of the surface hydroxyl groups are capped.

[0041] An asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand described herein, for example, a catalyst composition / spray-dried asymmetric metallocene composition can be contacted with an olefin under polymerization conditions to produce a polymer, such as a polyolefin polymer. The polymerization process may 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 may be used using known equipment and reaction conditions, such as 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, nonwovens and / or woven fabrics, extruded articles, and / or molded articles.

[0042] One or more embodiments provide that the polymer is manufactured using a gas-phase reactor system. One or more embodiments provide that, for example, as opposed to a series of reactors, a single gas-phase reactor is utilized. In other words, the polymerization reaction occurs only within one reactor. For example, the polymer can be manufactured using a fluidized bed reactor. Gas-phase reactors are known, and known components may be utilized in the fluidized bed reactor.

[0043] As used herein, an “olefin,” which may be referred to as an “alkene,” refers to a straight-chain, branched-chain, or cyclic compound that contains carbon and hydrogen and has at least one double bond. As used herein, when a polyolefin, polymer, and / or copolymer is said to contain an olefin, for example, be made from an olefin, the olefin present in such polymer or copolymer is a polymerized form of the olefin. For example, when a copolymer is said to have an ethylene content of 75 wt% to 95 wt%, the polymer units in the copolymer are derived from ethylene in the polymerization reaction, and it is understood that the derived units are present at 75 wt% to 95 wt% based on the total weight of the polymer. A higher α-olefin means an α-olefin having 3 or more carbon atoms.

[0044] The 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 from only olefin monomers (e.g., produced from 100% by weight of ethylene or 100% by weight of propylene). Alternatively, polyolefins produced using the compositions discussed herein include 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, in particular, ethylene-based polymers having at least 50% by weight of ethylene, such as ethylene-1-butene, ethylene-1-hexene, and ethylene-1-octene copolymers. One or more embodiments provide that the polymer may contain 50 to 99.9% by weight of units derived from ethylene, based on the total weight of the polymer. All individual values and subranges from 50 to 99.9% by weight are included. For example, the polymer may contain units derived from ethylene from a lower limit of 50, 60, 70, 80, or 90% by weight of ethylene to an upper limit of 99.9, 99.7, 99.4, 99, 96, 93, 90, or 85% by weight of ethylene, based on the total weight of the polymer. The polymer may contain 0.1 to 50% by weight of units derived from comonomers, based on the total weight of the polymer. One or more embodiments provide that ethylene is utilized as a monomer and hexene is utilized as a comonomer.

[0045] As described above, the polymers produced 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 sub-ranges of 10 to 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.

[0046] The fluidized bed reactor can have an ethylene partial pressure of 30 to 250 pounds per square inch (psi). All individual values and sub-ranges of 30 to 250 are included. 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.

[0047] One or more embodiments provide that ethylene is utilized as the monomer and hexene is utilized as the comonomer. The fluidized bed reactor can have a comonomer to ethylene molar ratio, such as C6 / C2, of 0.0001 to 0.100. All individual values and sub-ranges of 0.0001 to 0.100 are included. For example, the fluidized bed reactor can 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.

[0048] When hydrogen is utilized in the polymerization process, the fluidized bed reactor can have, for example, a hydrogen to ethylene molar ratio (H2 / C2) of 0.00001 to 0.90000. All individual values and sub-ranges of 0.00001 to 0.90000 are included. For example, the fluidized bed reactor can have an 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 hydrogen is not utilized.

[0049] 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 oven section of the autosampler was set at 160 °C and the column section was set at 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, which contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume employed was 200 microliters and the flow rate was 1.0 milliliter / minute.

[0050] Calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards with molecular weights in the range of 580 to 8,400,000 g / mol, placed in six "cocktail" mixtures having at least one order of magnitude spacing between individual molecular weights. The standards were purchased from Agilent Technologies. For molecular weights above 1,000,000, the polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent, and for molecular weights below 1,000,000, at 0.05 grams in 50 milliliters of solvent. The polystyrene standards were pre-dissolved at 80 °C with gentle stirring for 30 minutes, then cooled, and the room temperature solution was transferred to the autosampler dissolution oven at 160 °C and cooled for 30 minutes. The peak molecular weight of the polystyrene standards was converted to polyethylene molecular weight 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 ポリスチレン ) B (Equation 1) where M is the molecular weight, A has a value of 0.4061, and B is equal to 1.0.

[0051] A fifth-degree polynomial was used to fit each polyethylene equivalent calibration point.

[0052] The total plate number of the GPC column set was performed using decane introduced into the blank sample via a micropump controlled by a PolymerChar GPC-IR system. The plate number of the chromatographic system should exceed 18,000 for four Agilent "Mixed A" 30 cm 20 micron linear mixed-bed columns.

[0053] Samples were prepared in a semi-automatic mode using PolymerChar's "Instrument Control" software, with a target sample weight of 2 mg / ml. Solvent (containing 200 ppm BHT) was added to vials with septum caps pre-nitrogen sparged via a PolymerChar high-temperature autosampler. Samples were dissolved at 160 °C for 2 hours under "low-speed" shaking.

[0054] Mn (GPC) , Mw (GPC) and Mz (GPC) were calculated based on GPC results using PolymerChar's GPCONE software, an IR chromatogram with the baseline subtracted 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, according to Equations 2 - 4, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph.

[0055]

Equation

[0056] To monitor the deviation over time, a flow marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow marker (FM) was the respective decane peak (RV (FM試料)) within a narrow standard calibration (RV (FM較正済み) ) By matching the decapeak within with RV, the pump flow rate (flow rate (公称) ) of each sample was used to linearly calibrate. Then, any change in the time of the deca marker peak is presumed to be related to a linear shift in the flow rate (flow rate (有効) ) throughout the run. After calibrating the system based on the peak of the flow marker, the effective flow rate (relative to the narrow standard calibration) is calculated as shown in Equation 5. The processing of the flow velocity marker peak was performed via PolymerChar's GPCONE software. The acceptable flow rate correction should be such that the effective flow rate should be within ±0.5% of the apparent flow rate.

[0057] Flow rate (effective) = Flow rate (nominal) * (RV (FM calibrated) / RV (FM sample)) (Equation 5)

[0058] IR5 GPC octene composition correction. The calibration of the quantification of the IR5 detector was performed using at least 10 ethylene-based polymer standards (octene as comonomer) produced by single-site metallocene catalysts from a single reactor (polyethylene homopolymers and ethylene / octene copolymers) in a solution process with a narrow SCB distribution in the range of homopolymer (0 SCB / total 1000 carbon atoms) to approximately 40 SCB / total 1000 carbon atoms (where total C = carbon in the main chain + carbon in the branches) and known comonomer content ( 13 Measured by C NMR Method, Qiu et al., Anal. Chem. 2009, 81, 8585 - 8589). Each standard had a weight average molecular weight of 36,000 g / mol to 126,000 g / mol 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.

[0059]

Table 1

[0060] "Area Response minus the Baseline of the IR5 Methyl Channel Sensor" versus "Area Response minus the Baseline of the IR5 Measurement Channel Sensor" "IR5 Area Ratio (or "IR5 メチルチャネル面積 / IR5 測定チャネル面積 ")" (Standard filters and filter wheels supplied by PolymerChar: Part Number IR5_FWM01 are included as part of the GPC-IR instrument) was calculated for each of the "Copolymer" standards. A linear fit of weight % comonomer frequency versus "IR5 Area Ratio" was constructed in the form of Equation 6 below. Weight % 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 "weight % comonomer" at zero "IR5 Area Ratio", A1 is the slope of "weight % comonomer" versus "IR5 Area Ratio", and represents the increase in weight % comonomer as a function of "IR5 Area Ratio". The IR5 Area Ratio is equal to the IR5 height ratio for narrow PDI and narrow SCBD standard materials.

[0061] The comonomer distribution or short-chain branch distribution in an ethylene / α-olefin copolymer can be characterized as either normal (also called having a Ziegler-Natta distribution), inverse, or flat. Some of the reported methods are utilized to quantify the broad orthogonal composition distribution (BOCD). In this specification, a simple linear fitting is utilized such that the positive or inverse 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 composition GPC measurements, with the x-axis line being Log(MW) and the y-axis line being the weight percent of the comonomer. An inverse comonomer distribution is defined when MWCDI > 0, and a normal comonomer distribution is defined when MWCDI < 0. When MWCDI = 0, the comonomer distribution is said to be flat. Additionally, 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 a larger MWCDI value has a larger inverse comonomer distribution. For example, as reported in Tables 1 - 3 respectively, Examples 1 - 2 have an increased BOCD compared to Comparative Example A - 2. Polymers with a relatively large MWCDI, i.e., a BOCD, can provide improved physical properties, such as improved film properties, compared to polymers with a relatively small MWCDI.

[0062] The polymers produced from the compositions disclosed herein can have an MWCDI of 0.10 to 10.00. All individual values and subranges from 0.10 to 10.00 are included. For example, the polymer can have an 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.

[0063] The polymers produced from the compositions disclosed herein can have a density of 0.8700 to 0.9700 g / cm 3 . 0.8700 to 0.9700 g / cm 3includes all individual values and sub - ranges, for example, the polymer has a density of 0.8700, 0.9000, 0.9100, 0.9150, 0.9200, or 0.9250 g / cm 3 from a lower limit of 0.9700, 0.9600, 0.9500, 0.9450, 0.9350, or 0.9300 g / cm 3 to an upper limit. The density can be determined according to ASTM D792.

[0064] The polymers produced from the compositions disclosed herein can have a weight - average molecular weight (Mw) of 10,000 to 1,000,000 g / mol. All individual values and sub - ranges from 10,000 to 1,000,000 g / mol are included. For example, the polymer can have an Mw from a lower limit of 10,000, 50,000, or 100,000 g / mol to an upper limit of 1,000,000, 750,000, or 500,000 g / mol. Mw can be determined by gel permeation chromatography (GPC) as is known in the art. GPC is discussed herein.

[0065] The polymers produced from the compositions disclosed herein can have a number - average molecular weight (Mn) of 5,000 to 300,000 g / mol. All individual values and sub - ranges from 5,000 to 300,000 g / mol are included. For example, the polymer can have an Mn from a lower limit of 5,000, 20,000, or 40,000 g / mol to an upper limit of 300,000, 250,000, or 200,000 g / mol. Mn can be determined by GPC as described below.

[0066] The polymers produced using the compositions disclosed herein can have a Z - average molecular weight (Mz) of 40,000 to 2,000,000 g / mol. All individual values and sub - ranges from 40,000 to 2,000,000 g / mol are included. For example, the polymer can have a temperature from a lower limit of 40,000, 100,000, or 250,000 g / mol to an upper limit of 2,000,000, 1,800,000, or 1,650,000 g / mol. Mz can be determined by GPC.

[0067] The polymers produced using the compositions disclosed herein may have a weight-average molecular weight to number-average molecular weight ratio (Mw / Mn) of from 2.00 to 6.00. All individual values and subranges from 2.00 to 6.00 are included; for example, the polymer may have an Mw / Mn from a lower limit of 2.00, 2.50, or 3.00 to an upper limit of 6.00, 5.50, or 4.50.

[0068] Some aspects of the present disclosure are provided as follows.

[0069] Aspect 1 is an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand represented by Structure (I),

[0070]

Chemical formula

[0071] Aspect 2 provides an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand according to Aspect 1, wherein each X is, independently, a leaving group selected from halogen, (C1-C5) alkyl, CH2SiMe3, and benzyl.

[0072] Aspect 3 provides an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand according to any one of Aspects 1-2, wherein each X is Cl represented by Structure (II).

[0073]

Chemical formula

[0074] Aspect 4 provides an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand according to any one of claims 1 to 2, wherein each X is CH3 represented by structure (III).

[0075]

Chem.

[0076] Aspect 5 is a method for synthesizing an asymmetric metallocene according to any one of Aspects 1 to 3, wherein each X is Cl, wherein the zirconium complex is contacted with an alkali metal complex, and the alkali metal complex is represented by the following structure,

[0077]

Chem.

[0078]

Chem.

[0079] Aspect 5 is a method for synthesizing an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand according to any one of Aspects 1 to 3, wherein each X is Cl, wherein the zirconium complex is contacted with an alkali metal complex, and the alkali metal complex is represented by the following structure,

[0080]

Chem.

[0081]

Chemical formula

[0082] Aspect 6 is a method for synthesizing any one of the asymmetric metallocenes of Aspects 1 to 3, wherein each X is Cl, contacting the zirconium complex with an alkali metal complex, wherein the alkali metal complex is represented by the following structure,

[0083]

Chemical formula

[0084]

Chemical formula

[0085] Aspect 7 provides a method according to any one of Aspects 5 to 6, which includes contacting an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand with 2 molar equivalents of an organomagnesium halide of the formula RMg(halide) or 1 molar equivalent of R2Mg (wherein R is (C1 - C5)alkyl, CH2SiMe3, or benzyl, and the halide is Cl or Br), producing an asymmetric metallocene of structure (I), and each X is (C1 - C5)alkyl, CH2SiMe3, or benzyl.

[0086] Aspect 8 provides a metallocene catalyst composition comprising an asymmetric zirconium metallocene having any one of the isobutylcyclopentadienyl ligands of Aspects 1 to 4, or an asymmetric metallocene produced by any one of the methods of the claim aspects, and an activator (e.g., an alkylaluminoxane such as methylaluminoxane).

[0087] Aspect 9 provides the metallocene catalyst composition of Aspect 8, further comprising a carrier (e.g., silica such as hydrophobic fumed silica or dehydrated silica).

[0088] Aspect 10 provides the metallocene catalyst composition of Aspect 9, wherein the composition is a spray-dried metallocene catalyst composition.

[0089] Aspect 11 is a method for producing any one of the metallocene catalyst compositions of Aspects 9 to 10, comprising contacting an asymmetric metallocene with an activator rather than a carrier to obtain a metallocene catalyst composition without a carrier, or contacting an asymmetric metallocene with an activator and a carrier to obtain a metallocene catalyst composition having a carrier, or contacting an asymmetric metallocene with an activator and a carrier in an inert solvent to obtain a suspension thereof, and spray-drying the suspension to obtain a spray-dried metallocene catalyst composition, or contacting an asymmetric metallocene in an inert solvent with a supported or spray-dried activator (or a slurry thereof) to obtain a spray-dried metallocene catalyst composition.

[0090] Aspect 12 is a method for producing a polyolefin polymer, comprising polymerizing at least one olefin monomer with any one of the metallocene catalyst compositions of Aspects 8 to 10, or a metallocene catalyst composition produced by the method of Aspect 11, preferably wherein the at least one olefin monomer comprises ethylene and, optionally, a comonomer selected from the group consisting of propene and (C4 - C 20 ) α-olefin.

[0091] Aspect 13 provides a method of Aspect 12, wherein 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. Preferably, the comonomer is selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

[0092] Aspect 14 provides a polyolefin polymer produced by the method according to any one of Aspects 12 to 13.

Examples

[0093] 5-(2-Methylpropylidene)cyclopenta-1,3-diene, which can be represented by the following formula,

[0094]

Chemical formula

[0095] Isobutylcyclopentadienyllithium, which can be represented by the following formula,

[0096]

Chemical formula

[0097] Et2O (250 mL) was added to a container. 5-(2-Methylpropylidene)cyclopenta-1,3-diene (16.0 g, 133 mmol) was added to the contents of the container with stirring. LiAlH4 (33 mL, 4M Et2O solution) was added dropwise to the contents of the container 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 became very faintly yellow. The product isobutylcyclopentadienyllithium, which was observed to be a white solid, was recovered by filtration, washed with Et2O, and dried under vacuum (13.7 g, 80%).

[0098] The asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand, which is (cyclopentadienyl)(isobutylcyclopentadienyl)zirconium dichloride that can be represented by the following formula in Example 1-1,

[0099]

Chemical formula

[0100] was synthesized as follows. A solution of isobutylcyclopentadienyllithium (0.11 g, 0.76 mmol) in THF (5 mL) was added to CpZrC in THF (5 mL) I3A solution of [[ID=]] (zirconium complex, 0.2 g, 0.76 mmol, obtained from Boulder Scientific Company) was slowly added to a vial containing the solution, and the mixture was stirred at room temperature for about 12 hours. Then, the solvent was removed under vacuum, and the residue was redissolved in toluene (10 mL) and filtered through a syringe filter. The solution was concentrated to about 2 mL under vacuum. The addition of pentane (10 mL) resulted in the formation of a white precipitate. The solid was collected, washed with pentane (2 × 5 mL), and dried under vacuum to obtain Example 1-1 (0.21 g, 80%). 1 H NMR (400 MHz, Benzene-d6) δ 5.94 (s, 4H), 5.85 (t, J = 2.76 Hz, 2H), 5.66 (t, J = 2.67 Hz, 2H), 2.51 (d, J = 7.18 Hz, 2H), 1.60 (tq, 1H), 0.78 (d, J = 6.65 Hz, 6H).

[0101] The (cyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride, which can be represented by the following formula, of Comparative Example A-1 was

[0102] [Chemical formula] Prepared as follows. A solution of n-butylcyclopentadienyllithium (0.098 g, 0.76 mmol) in THF (5 mL) was slowly added to a vial containing a solution of CpZrCl3 (0.2 g, 0.76 mmol) in THF (5 mL), and the mixture was stirred at room temperature for about 12 hours. Then, the solvent was removed under vacuum, and the residue was redissolved in toluene (10 mL) and filtered through a syringe filter. Then, the filtrate was concentrated to about 2 mL under vacuum. The addition of pentane (10 mL) resulted in the formation of a white precipitate. The solid was collected, washed with pentane (2 × 5 mL), and dried under vacuum to obtain Comparative Example A-1 (0.21 g, 79%). 11H NMR (400 MHz, benzene-d6) δ 5.94 (s, 4H), 5.86 (t, J = 2.6 Hz, 2H), 5.66 (t, J = 2.7 Hz, 2H), 2.61 (t, J = 7.93 Hz, 2H), 1.40 (m, 2H), 1.21 (m, 2H), 0.83 (t, J = 7.3 Hz, 3H).

[0103] Examples 1-2, which are spray-dried compositions, were prepared as follows. Inside a nitrogen-purged glove box, Cabosil TS-610 hydrophobic fumed silica (1.34 g) is slurried in toluene (34 g) until thoroughly dispersed. Then, 10.7 g of a 10 wt% solution of MAO in toluene is added. The mixture is stirred for 15 minutes. Then, Example 1-1 (0.028 g) is added. The mixture is stirred for about 45 minutes. Using a Buchi Mini Spray Dryer B-290 with the following operating parameters: set temperature 185 °C, outlet temperature 100 °C, aspirator 95, and pump speed 150 revolutions per minute (rpm), the mixture is spray-dried to obtain Example 1-2.

[0104] Comparative Example A-2, which is a spray-dried composition, was prepared as follows. Inside a nitrogen-purged glove box, Cabosil TS-610 hydrophobic fumed silica (1.34 g) is slurried in toluene (34 g) until thoroughly dispersed. Then, 10.7 g of a 10 wt% solution of MAO in toluene is added. The mixture is stirred for 15 minutes. Then, Comparative Example A-1 (0.028 g) is added. The mixture is stirred for about 45 minutes. Using a Buchi Mini Spray Dryer B-290 with the following operating parameters: set temperature 185 °C, outlet temperature 100 °C, aspirator 95, and pump speed 150 revolutions per minute (rpm), the mixture is spray-dried to result in Comparative Example A-2.

[0105] The polymerization was carried out as follows. For each polymerization, dry NaCl (200 g) was charged into 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 for 1 hour under a nitrogen stream. Subsequently, the reactor was 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 contents of the reactor were stirred. The reactor was pre-filled with hydrogen, ethylene, and 1-hexene to the desired pressure. Once a steady state was reached, the catalyst was charged into the reactor (at the temperature shown 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 kept constant. At the end of 60 minutes of polymerization, the reactor was cooled, vented, and opened. The resulting mixture was washed with water and methanol and dried. The polymerization conditions are shown in Tables 1 to 3.

[0106] For the polymers produced in Examples 3 to 9 and Comparative Examples C to O, several properties were determined. The results are reported in Tables 2 and 3. Catalyst productivity (polymer (grams) / catalyst (grams)-hour) was determined as the ratio of the polymer produced to the amount of catalyst added to the reactor. The melt index (I2) was determined according to ASTM D1238 (190 °C, 2.16 kg), the melt index (I5) was determined according to ASTM D1238 (190 °C, 5 kg), and the melt index (I 21 ) was determined according to ASTM D1238 (190 °C, 21.6 kg). The molecular weight comonomer distribution index (MWCDI) was determined as discussed herein. The melting temperature was determined using differential scanning calorimetry according to ASTM D 3418-08, using a scan rate of 10 °C / min for a 10 mg sample and using the second heating cycle to determine T m . M w , M n , M z , M w / M n (PDI), and M z / M wIt was determined as described above in the detailed description. The comonomer content incorporated into the polymer, for example, 1 - hexene, was determined by high - speed FT - IR spectroscopy for the dissolved polymer in GPC measurement as described above in the detailed description.

[0107]

Table 2

[0108]

Table 3

[0109]

Table 4

[0110] The data in Tables 1 - 3 show that the polymers produced in Examples 1 - 2 had an improved, i.e., larger molecular weight comonomer distribution index (MWCDI), compared to the polymers produced in Comparative Example A - 2. The data in Tables 1 - 3 show that the polymers produced in Examples 1 - 2 had a molecular weight comonomer distribution index (MWCDI) greater than 0.

[0111] In addition, the data in Tables 1 - 3 show that the polymers produced in Examples 1 - 2 had an improved, i.e., larger comonomer incorporation (C6 wt%), compared to the polymers produced in Comparative Example A - 2.

Claims

1. An asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand represented by Structure (I), 【Chemical 1】 wherein each X is, independently, a leaving group, and the asymmetric zirconium metallocene has an isobutylcyclopentadienyl ligand.

2. Each X is, independently, a leaving group selected from halogen, (C １ ~C ５ )alkyl, CH ２ SiMe ３ , and benzyl, the asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand according to claim 1.

3. The asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand according to any one of Claims 1 to 2, wherein each X is Cl represented by Structure (II). 【Chemical Formula 2】

4. Each X is CH represented by Structure (III) ３ The asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand according to any one of claims 1 to 2, wherein... 【Chemical Formula 3】

5. A method for synthesizing an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand according to any one of Claims 1 to 3, wherein each X is Cl, the zirconium complex is contacted with an alkali metal complex, and the alkali metal complex is represented by the following structure, 【Chemical Formula 4】 wherein M' is lithium, sodium, or potassium, and the zirconium complex is represented by the following structure. 【Chemical Formula 5】 In the formula, R １ is H, and the method includes producing an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand.

6. A method for synthesizing an asymmetric metallocene according to any one of Claims 1 to 3, wherein each X is Cl, the zirconium complex is contacted with an alkali metal complex, and the alkali metal complex is represented by the following structure, 【Chemical Formula 6】 wherein M' is lithium, sodium, or potassium, and R １ is H, and the zirconium complex is represented by the following structure. 【Chemical Formula 7】 A method comprising manufacturing an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand.

7. The asymmetric zirconium metallocene having the isobutylcyclopentadienyl ligand is contacted with 2 molar equivalents of an organomagnesium halide of the formula RMg (halide) or 1 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 produce an asymmetric metallocene of structure (I), each X being (C １ -C ５ ) alkyl, CH ２ SiMe ３ , or benzyl, the method according to any one of claims 5 to 6.

8. A metallocene catalyst composition comprising an asymmetric zirconium metallocene having an isobutylcyclopentadienyl ligand according to any one of Claims 1 to 4, or an asymmetric metallocene produced by the method according to any one of Claims 5 to 7, and an activator.

9. The metallocene catalyst composition according to Claim 8, further comprising a carrier.

10. The metallocene catalyst composition according to Claim 9, wherein the composition is a spray-dried metallocene catalyst composition.

11. A method for producing the metallocene catalyst composition according to any one of claims 9 to 10, comprising contacting the asymmetric metallocene with the activator rather than a carrier to obtain a metallocene catalyst composition without a carrier, or contacting the asymmetric metallocene with the activator and the carrier to obtain a metallocene catalyst composition having a carrier, or contacting the asymmetric metallocene with the activator and the carrier in an inert solvent to obtain a suspension thereof, and spray-drying the suspension to obtain a spray-dried metallocene catalyst composition, or contacting the asymmetric metallocene in an inert solvent with a supported or spray-dried activator (or a slurry thereof) to obtain the spray-dried metallocene catalyst composition, or contacting an asymmetric 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.

12. A method for producing a polyolefin polymer, At least one olefin monomer is polymerized with any one of the metallocene catalyst compositions according to any one of claims 8 to 10 or the metallocene catalyst composition produced by the method according to claim 11 to produce the polyolefin polymer, preferably, the at least one olefin monomer comprises ethylene and, optionally, a comonomer selected from the group consisting of propene and (C ４ -C ２０ )α-olefin, method.

13. wherein the at least one olefin monomer comprises ethylene and the 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, the method according to claim 12.

14. A polyolefin polymer produced by the method according to any one of claims 12 to 13.

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