Asymmetric metallocene having an isobutylcyclopentadienyl ligand

Abstract

Embodiments of the present disclosure relate to asymmetric metallocenes having isobutylcyclopentadienyl ligands, compositions comprising such asymmetric metallocenes, and methods of using compositions comprising asymmetric metallocenes.

Description

Technical Field

[0001] Embodiments of the present disclosure relate to an asymmetric metallocene, a catalyst composition comprising the asymmetric metallocene, 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 metallocene represented by structure (I),

[0005]

Chemical Formula

[0006] An asymmetric metallocene catalyst composition comprising an asymmetric metallocene and an activator.

[0007] A method for producing an asymmetric metallocene catalyst composition, comprising contacting an asymmetric metallocene with an activator.

[0008] A method for producing a polyolefin polymer, comprising polymerizing at least one olefin monomer with an asymmetric metallocene catalyst composition to produce a polyolefin polymer.

Brief Description of the Drawings

[0009]

Figure 1A

Figure 1B

Modes for Carrying Out the Invention

[0010] Asymmetric metallocenes having isobutylcyclopentadienyl ligands are discussed herein. Advantageously, these asymmetric metallocenes can be utilized, for example, to produce catalyst compositions. These catalyst compositions can be utilized to produce polymers having an improved, i.e., larger, molecular weight comonomer distribution index (MWCDI) compared to other polymers produced from other metallocenes. These polymers are desirable for many applications, particularly those involving films. Thus, it is advantageous to provide an improved MWCDI. Such polymers are advantageous for many applications.

[0011] The asymmetric metallocene has an isobutylcyclopentadienyl ligand and can be represented by Structure (I),

[0012]

Chemical Formula

[0013] One or more embodiments of the present disclosure assume that M is Hf. One or more embodiments of the present disclosure assume that M is Zr.

[0014] For example, one or more embodiments assume that M is Hf, and the asymmetric metallocene is represented by structure (Ia),

[0015]

Chemical formula

[0016] One or more embodiments assume that M is Zr and the asymmetric metallocene has structure (Ib):

[0017]

Chemical formula

[0018] One or more embodiments of the present disclosure define that the ligand of the cyclopentadienyl ring having an isobutylcyclopentadienyl ligand represented by structure (I) is R 1 is different from the ligand of the cyclopentadienyl ring containing. Thus, the asymmetric metallocenes discussed herein can be considered to have non-identical ligands. As an example, an embodiment defines that R 1 is not an isobutyl group.

[0019] One or more embodiments define that R 1 is (C1-C3) alkyl, (C4) alkyl excluding 2-methylpropyl, or (C5) alkyl. One or more embodiments define that R 1 is (C5) alkyl. One or more embodiments define that R 1 is (C4) alkyl excluding 2-methylpropyl. One or more embodiments define that R 1 is (C1-C3) alkyl. One or more embodiments define that R 1 is (C1-C2) alkyl. One or more embodiments define that R 1 is (C3) alkyl. (C3) alkyl may be branched or linear. As used herein, "Pr" and "n-Pr" refer to CH2CH2CH3. One or more embodiments of the present disclosure define that R 1 is (C2 alkyl. One or more embodiments of the present disclosure define that R 1is defined as (C2) alkyl. One or more embodiments of the present disclosure have R 1 defined as (C3) alkyl, ethyl, or methyl, where (C3) alkyl is selected from 1-methylethyl and propyl.

[0020] 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.

[0021] 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 substituted derivatives thereof. One or more embodiments include hydrides, halide 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)Alkyl aryl carboxylate, (C1-C6) fluoroalkyl, (C2-C6) fluoroalkenyl, and (C7-C 18 )fluoroalkyl aryl. 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 )alkyl aryl, substituted (C1-C 12 )alkyl, substituted (C6-C 12 )aryl, substituted (C7-C 20 )alkyl aryl, and (C1-C 12 )heteroatom-containing alkyl, (C1-C 12 )heteroatom-containing aryl, and (C1-C 12 )heteroatom-containing alkyl aryl. One or more embodiments include chloride, fluoride, (C1-C6) alkyl, (C2-C6) alkenyl, (C7-C 18 )alkyl aryl, halogenated (C1-C6) alkyl, halogenated (C2-C6) alkenyl, and halogenated (C7-C 18 )alkyl aryl. 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).

[0022] 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 may be a leaving group selected from the group consisting of. In one or more embodiments, X is methyl.

[0023] The asymmetric metallocenes discussed herein can be prepared by contacting an Hf complex or a Zr complex with an alkali metal complex to produce an asymmetric metallocene. By way of example, the alkali metal complex can be, inter alia, a lithium complex such as iso-butylcyclopentadienyllithium, methylcyclopentadienyllithium, ethylcyclopentadienyllithium, n-propylcyclopentadienyllithium, and the like. The asymmetric metallocenes discussed herein can be prepared, for example, by a process using conventional solvents, reaction conditions, reaction times, and isolation procedures used to prepare known metallocenes.

[0024] The alkali metal complex can be represented by the following structure,

[0025]

Chemical formula

[0026] One or more embodiments define that the hafnium complex can be represented by the following structure,

[0027]

Chemical formula

[0028] One or more embodiments define that the hafnium complex or zirconium complex can be represented by the following structure,

[0029]

Chemical formula

[0030] The alkali metal complex can be represented by the following structure,

[0031]

Chemical formula

[0032] One or more embodiments define that the hafnium complex or zirconium complex can be represented by the following structure,

[0033]

Chemical formula

[0034] One or more embodiments define that a hafnium complex or a zirconium complex can be represented by the following structure,

[0035] [Chemical formula] In the formula, M is Hf or Zr, respectively.

[0036] One or more embodiments provide, for example, a method for producing an asymmetric metallocene in which each X is Cl. The method involves contacting an asymmetric metallocene with 2 molar equivalents of an organomagnesium halide of the formula RMg(halide) or 1 molar equivalent of an organomagnesium halide of the formula R2Mg(halide) (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 (C1-C5) alkyl, CH2SiMe3, or benzyl. One or more embodiments define that X is CH3.

[0037] As used herein, all references to the Periodic Table of the Elements and its groups are 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 by a reference to the previous IUPAC system, which is also shown in Roman numerals, or unless otherwise specified.

[0038] 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 alkyl.

[0039] As used herein, "alkenyl" includes linear, branched, and cyclic olefinic groups lacking one hydrogen. Alkynyl groups include linear, branched, and cyclic acetylene groups lacking one hydrogen group.

[0040] As used herein, "aryl" groups include phenyl, naphthyl, pyridyl, and other groups whose molecules have a ring structure characteristic of benzene, naphthylene, phenanthrene, anthracene, etc. The "aryl" group is 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". The "arylalkyl" group is an alkyl group having an aryl group hanging therefrom. The "aralkyl" group is (C7~C 20 ) It is understood that it can be an aralkyl group. "Alkylaryl" is an aryl group having one or more alkyl groups hanging therefrom.

[0041] 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".

[0042] 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, it can contain one or more of the same or different heteroatoms, and 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).

[0043] As used herein, the term "substituted" means that one or more hydrogen atoms in the parent structure are independently replaced by a substituent atom or group.

[0044] The asymmetric metallocenes discussed herein can be utilized to produce catalyst compositions. These asymmetric metallocene compositions include an asymmetric 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, the term "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. For example, this can include the extraction of at least one leaving group from the metal center of the complex / catalyst component, such as the "X" group described herein. The activator is sometimes referred to as a "cocatalyst". As used herein, the term "leaving group" refers to one or more chemical moieties that are bonded to a metal atom and can be extracted by an activator, thus generating a species that is active for olefin polymerization. Various catalyst compositions, for example, 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.

[0045] The asymmetric metallocenes discussed herein can be utilized to produce spray-dried compositions. As used herein, the term "spray-dried composition" refers to a composition that includes 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.

[0046] In one or more embodiments, the spray drying process may include atomizing a composition comprising an asymmetric metallocene having an isobutylcyclopentadienyl ligand. Some 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.

[0047] 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 some 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.

[0048] 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 metallocene having an isobutylcyclopentadienyl ligand as discussed herein. Such a solution can typically be prepared, for example, in an inert hydrocarbon solvent and may sometimes be referred to as a trim solution. Such a spray-dried composition consisting of contacting a trim solution of an asymmetric metallocene with spray-dried activator particles, for example, spray-dried MAO, may be produced in situ in the supply line leading to the gas-phase polymerization reactor by contacting the trim solution with a slurry of the spray-dried activator particles, typically in mineral oil.

[0049] Various spray drying conditions may be utilized for different applications. For example, the spray drying process may use a drying temperature of 75 to 185 °C. Other drying temperatures are possible and the temperature may depend on the metallocene and activator. Different sizes may be obtained by utilizing orifices of various sizes of the atomizing nozzles employed during the spray drying process. Alternatively, with other types of atomizers such as disks, different 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.

[0050] The catalyst compositions such as the asymmetric metallocenes discussed herein, e.g., spray dried asymmetric metallocene compositions, 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 comprises an activator. As used herein, "activator" refers to any supported or unsupported compound or combination of compounds that can activate a complex or catalyst component, e.g., by generating a cationic species of the catalyst component to provide a catalyst. The activator may also be referred to as a "cocatalyst". The activator can include a Lewis acid or non-coordinating ionic activator or ionizing activator, or a Lewis base, an aluminum alkyl, and / or any other compound including a conventional type promoter. Particularly, methylaluminoxane (MAO) and modified methylaluminoxane (MMAO) are included as activators. One or more embodiments provide that the activator is methylaluminoxane. The activation conditions are well known in the art. Known activation conditions may be utilized.

[0051] The molar ratio of metal in the activator, such as aluminum, to Hf or Zr in an asymmetric 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 define that the molar ratio of the activator to Hf or Zr in the asymmetric metallocene is at least 75:1. One or more embodiments define that the molar ratio of the activator to Hf or Zr in the asymmetric metallocene is at least 100:1. One or more embodiments define that the molar ratio of the activator to Hf or Zr in the asymmetric metallocene is at least 150:1.

[0052] The asymmetric 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. Using a carrier can be achieved by any technique used in the art. One or more embodiments provide that a spray drying process is utilized. The carrier may be functionalized. One or more embodiments provide that the spray dried composition contains a carrier.

[0053] The "carrier", which may also be referred to as a "support", refers to any carrier material including porous carrier materials 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 materials, or mixtures thereof.

[0054] 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. In addition, combinations of these carrier materials, such as silica-chromium, silica-alumina, silica-titania, etc. can be used. One or more embodiments provide that the carrier is hydrophobic fumed silica. Further 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.

[0055] The asymmetric metallocenes discussed 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 carried out 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.

[0056] 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 a fluidized bed reactor.

[0057] 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 a polymer or copolymer is in 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 a 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.

[0058] 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 those 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, the polyolefins produced using the compositions discussed herein can be 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 can include units derived from 50 to 99.9% by weight of 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 can include units derived from ethylene from a lower limit of 50, 60, 70, 80, or 90% by weight of ethylene, based on the total weight of the polymer, to an upper limit of 99.9, 99.7, 99.4, 99, 96, 93, 90, or 85% by weight of ethylene. The polymer can include units derived from 0.1 to 50% by weight of comonomer, 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.

[0059] 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 subranges from 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.

[0060] The fluidized bed reactor can have an ethylene partial pressure of 30 - 250 pounds per square inch (psi). All individual values and sub - ranges of 30 - 250 are included. For example, the fluidized bed reactor can have an ethylene partial pressure ranging 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.

[0061] One or more embodiments provide that ethylene is utilized as a monomer and hexene is utilized as a comonomer. The fluidized bed reactor can have a comonomer - to - ethylene molar ratio, for example, C6 / C2, of 0.0001 - 0.100. All individual values and sub - ranges of 0.0001 - 0.100 are included. For example, the fluidized bed reactor can have a comonomer - to - ethylene molar ratio ranging 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.

[0062] 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 - 0.90000. All individual values and sub - ranges of 0.00001 - 0.90000 are included. For example, the fluidized bed reactor can have an H2 / C2 ranging 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.

[0063] 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 chromatography 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 chromatography solvent used was 1,2,4-trichlorobenzene and 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.

[0064] Calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards having 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 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)),

[0065]

Number

[0066] A fifth-degree polynomial was used and applied to each polyethylene equivalent calibration point.

[0067] Using decane introduced into a blank sample via a micropump controlled by a PolymerChar GPC-IR system, the total plate number of the GPC column set was performed. The plate number of the chromatographic system should exceed 18,000 for four Agilent "Mixed A" 30 cm 20 micron linear mixed-bed columns.

[0068] The sample was prepared in a semi-automatic mode using PolymerChar's "Instrument Control" software, with a target weight of 2 mg / ml for the sample. Solvent (containing 200 ppm of BHT) was added to a vial with a septum cap pre-nitrogen-sparged through a PolymerChar high-temperature autosampler. The sample was dissolved for 2 hours under "low-speed" shaking at 160 °C.

[0069] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculations of were based on the GPC results using PolymerChar's GPCONE software, the IR chromatogram with the baseline subtracted at each equally spaced data collection point (i), and the 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.

[0070]

Equation

[0071] 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 used to linearly calibrate the pump flow rate (flow rate (FM試料) ) of each sample by matching each decane peak (RV (FM較正済み) ) in the sample with the decane peak within a narrow standard calibration (RV (公称) ). Subsequently, any change in the time of the decane marker peak is presumed to be related to a linear shift in the flow rate (flow rate (有効) ) over the entire 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 rate 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.

[0072] Flow rate (effective) = Flow rate (nominal) * (RV (FM calibrated) / RV (FM sample)) (Equation 5)

[0073] 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 single reactors (polyethylene homopolymers and ethylene / octene copolymers) in solution processes with a narrow SCB distribution in the range of homopolymer (0 SCB / total carbon atoms 1000) to approximately 40 SCB / total carbon atoms 1000 (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 measured by GPC in the range of 36,000 g / mol to 126,000 g / mol. 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.

[0074]

Table 1

[0075] "Area response minus the baseline of the IR5 methyl channel sensor" vs. "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 filter and filter wheel supplied by PolymerChar: Part Number IR5_FWM01 is included as part of the GPC-IR instrument) was calculated for each of the "copolymer" standards. A linear fit of weight % comonomer frequency vs. "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" vs. "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.

[0076] 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). Herein, 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 compositional GPC measurements, with the x-axis line being Log(MW) and the y-axis line being the weight percent of the comonomer. Figure 1A shows the data plots utilized to determine the MWCDI for Examples 1-2 (MWCDI = 5.85) and Comparative Example A-2 (MWCDI = 3.60) as shown in Table 1 of the Examples section of this application. Figure 1B shows the data plots utilized to determine the MWCDI for Examples 1-2 (MWCDI = 2.13) and Comparative Example A-2 (MWCDI = 1.67) as shown in Table 2 of the Examples section of this application.

[0077] The inverse comonomer distribution is defined when MWCDI > 0, and the 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. Comparing two polymers with MWCDI > 0, the polymer with the larger MWCDI value is defined to have a larger, i.e., increased BOCD. In other words, the larger the MWCDI value of a polymer, the larger the inverse comonomer distribution. For example, as reported in Table 1 and Table 2 respectively, Examples 1-2, Example 2-2, and Example 3-2 each have an increased BOCD compared to Comparative Example A-2. Polymers with a relatively large MWCDI, i.e., a BOCD, may provide improved physical properties, such as improved film properties, compared to polymers with a relatively small MWCDI.

[0078] The polymers produced with the compositions disclosed herein may have an MWCDI of 0.05 to 10.00. All individual values and subranges from 0.10 to 10.00 are included. For example, the polymer may have an MWCDI from a lower limit of 0.05, 0.10, 0.30, 0.50, or 1.00 to an upper limit of 10.00, 9.00, 8.00, 8.50, 8.35, 7.00, or 6.00. For example, one or more embodiments define that the polymer may have an MWCDI in other ranges, particularly 0.05 to 6.00, 0.10 to 2.00, 0.50 to 3.00, 1.00 to 7.00, or 1.00 to 6.00.

[0079] The polymers produced with the compositions disclosed herein may have a density of 0.8700 to 0.9700 g / cm 3 All individual values and subranges from 0.8700 to 0.9700 g / cm 3 are included. For example, the polymer may have a density from a lower limit of 0.8700, 0.9000, 0.9100, 0.9150, 0.9200, or 0.9250 g / cm 3 to an upper limit of 0.9700, 0.9600, 0.9500, 0.9450, 0.9350, or 0.9300 g / cm 3 The density may be determined in accordance with ASTM D792.

[0080] The polymers produced with the compositions disclosed herein may have a melt index (I2) of 0.0 to 10 dg / min. I2 may be determined in accordance with ASTM D1238 (190 °C, 2.16 kg). All individual values and subranges from 0.00 to 10 dg / min are included. For example, the polymer may have an I2 from a lower limit of 0.0, 0.05, 0.07, or 0.10 dg / min to an upper limit of 10, 5, or 3 dg / min.

[0081] The polymers produced with the compositions disclosed herein may have a melt index (I5) of 0.05 to 15 dg / min. I5 can be determined in accordance with ASTM D1238 (190 °C, 5 kg). All individual values and subranges from 0.05 to 15 dg / min are included. For example, the polymer may have an I5 from a lower limit of 0.05, 0.07, or 0.10 dg / min to an upper limit of 15, 10, or 5 dg / min.

[0082] The polymers produced with the compositions disclosed herein may have a melt index (I 21 ) of 0.05 to 25 dg / min. I 21 can be determined in accordance with ASTM D1238 (190 °C, 21.6 kg). All individual values and subranges from 0.05 to 25 dg / min are included. For example, the polymer may have an I 21 from a lower limit of 0.05, 0.07, or 0.10 dg / min to an upper limit of 25, 15, or 5 dg / min.

[0083] The polymers produced with the compositions disclosed herein may have a weight average molecular weight (Mw) of 10,000 to 1,000,000 g / mol. All individual values and subranges from 10,000 to 1,000,000 g / mol are included. For example, the polymer may 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 known in the art. GPC is discussed herein.

[0084] The polymers produced with the compositions disclosed herein may have a number average molecular weight (Mn) of 5,000 to 300,000 g / mol. All individual values and subranges of 5,000 to 300,000 g / mol are included. For example, the polymer may 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.

[0085] The polymers produced using the compositions disclosed herein may have a Z average molecular weight (Mz) of 40,000 to 2,000,000 g / mol. All individual values and subranges of 40,000 to 2,000,000 g / mol are included. For example, the polymer may 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.

[0086] The polymers produced using the compositions disclosed herein may have a weight average molecular weight to number average molecular weight ratio (Mw / Mn) of 2.00 to 6.00. All individual values and subranges of 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.

[0087] Some aspects of the present disclosure are provided as follows.

[0088] Aspect 1 is an asymmetric metallocene represented by structure (I),

[0089]

Chemical formula

[0090] Embodiment 2 is where M is Hf, and the asymmetric metallocene is represented by structure (Ia),

[0091]

Chemical formula

[0092] Embodiment 3 is where M is Zr, and the asymmetric metallocene is represented by structure (Ib),

[0093]

Chemical formula

[0094] wherein R 1 is as defined in claim 1, and each X is independently a leaving group selected from halogen, (C1-C5)alkyl, CH2SiMe3, and benzyl, to provide the asymmetric metallocene according to Embodiment 1.

[0095] Embodiment 4 is where R 1 is (C1-C3)alkyl, (C1-C3)alkyl is (C3)alkyl, ethyl or methyl, (C3)alkyl is selected from 1-methylethyl and n-propyl, or R 1 is (C4)alkyl other than 2-methylpropyl, or R 1 is (C5)alkyl, to provide the asymmetric metallocene according to any one of Embodiments 1-3.

[0096] Aspect 5 provides an asymmetric metallocene according to any one of Aspects 1 to 4, wherein each X is Cl or each X is CH3.

[0097] Aspect 6 is an asymmetric metallocene wherein the hafnium asymmetric metallocene represented by Structures (II) to (IV):

[0098]

Chem.

[0099]

Chem.

[0100] Aspect 7 is a method for synthesizing an asymmetric metallocene according to any one of Aspects 1 to 6, the method comprising, for producing an asymmetric metallocene, reacting a hafnium complex or a zirconium complex with an alkali metal complex, the alkali metal complex having the following structure:

[0101]

Chem.

[0102]

Chem.

[0103]

Chemical formula

[0104]

Chemical formula

[0105] Aspect 8 provides a method according to Aspect 7, including contacting an asymmetric metallocene 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) to produce an asymmetric metallocene of structure (I), and each X is (C1 - C5) alkyl, CH2SiMe3, or benzyl.

[0106] Aspect 9 provides a metallocene catalyst composition including an asymmetric metallocene according to any one of Aspects 1 - 6, or an asymmetric metallocene produced by the method of Aspect 7 or Aspect 8, and an activator (for example, an alkylaluminoxane such as methylaluminoxane).

[0107] Aspect 10 provides the metallocene catalyst composition according to aspect 9, further comprising a carrier (e.g., silica such as hydrophobic fumed silica or dehydrated silica).

[0108] Aspect 11 provides the metallocene catalyst composition according to aspect 10, wherein the composition is a spray-dried metallocene catalyst composition.

[0109] Aspect 12 is a method for producing the metallocene catalyst composition according to any one of aspects 9 to 11, comprising contacting an asymmetric metallocene with an activator rather than a carrier to obtain the metallocene catalyst composition according to aspect 9 without a carrier, or contacting an asymmetric metallocene with an activator and a carrier to obtain the metallocene catalyst composition according to aspect 10 having a carrier, and 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 the spray-dried metallocene catalyst composition according to aspect 11, or contacting an 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 according to aspect 11, comprising any one of the above.

[0110] Aspect 13 is a method for producing a polyolefin polymer, comprising polymerizing at least one olefin monomer with any one of the metallocene catalyst compositions according to any one of aspects 9 to 11 or the metallocene catalyst composition produced by the method according to aspect 12 to produce a polyolefin polymer, preferably, at least one olefin monomer comprising ethylene and optionally a comonomer selected from the group consisting of propene and (C4 - C 20 ) α-olefin.

[0111] Aspect 14 provides a method according to Aspect 13, 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, and preferably the comonomer is selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

[0112] Aspect 15 provides a polyolefin polymer produced by the method according to any one of Aspects 13 to 14.

Examples

[0113] 5-(2-Methylpropylidene)cyclopenta-1,3-diene, which can be represented by the following formula,

[0114]

Chemical formula

[0115] Isobutylcyclopentadienyllithium, which can be represented by the following formula,

[0116]

Chemical formula

[0117] 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, 4 M 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 collected by filtration, washed with Et2O, and dried under vacuum (13.7 g, 80%). [[ID=z18]]

[0118] The hafnium complex I, which can be represented by the following formula:

[0119]

Chemical formula

[0120] Hafnium(IV) chloride (0.33 g, 1.0 mmol) and bis(iso-butylcyclopentadienyl)hafnium(IV) dichloride (0.50 g, 1.0 mmol) were mixed in a large screw-cap container. The contents of the container changed to a viscous brown liquid upon heating. Colorless vapors began to appear on the side of the container at about 150 °C. At this point, the heating was adjusted to 150 °C. White solids began to form in the colorless vapor stream. After about 5 minutes, the container was removed from the heat and cooled under a nitrogen atmosphere. The white solid was scraped out of the container by hand and transferred to a second container. After removing most of the white solid, the container was placed under vacuum and reheated to 150 °C for 5 minutes. A second harvest of white solid was obtained and combined with the first set of isolated material to give Complex I (0.59 g, 72%). 1 H NMR (400 MHz, C6D6) δ 5.81 (t, J = 2.7 Hz, 2H), 5.75 (t, J = 2.7 Hz, 2H), 2.27 (d, J = 7.0 Hz, 3H), 1.35 (dq, J = 13.5, 6.7 Hz, 1H), 0.59 (d, J = 6.6 Hz, 8H).

[0121] 13 C NMR (101 MHz, C6D6) δ 134.94, 116.61, 116.04, 38.83, 30.18, 21.67. 13 C NMR (101 MHz, C6D6) δ 134.94, 116.61, 116.04, 38.83, 30.18, 21.67.

[0122] The hafnium complex II: (n-propylcyclopentadienyl)hafnium(IV) trichloride, dimethoxyethane adduct, which can be represented by the following formula:

[0123]

Chemical formula

[0124] Asymmetric metallocene which can be represented by the following formula and is Example 1-1:

[0125] [Chemical formula] <> was synthesized as follows.

[0126] (n-Propylcyclopentadienyl)hafnium trichloride, dimethoxyethane adduct (0.15 g, 0.311 mmol) and isobutylcyclopentadienyllithium (0.022 g, 0.311 mmol) were added to a container. Then, Et2O was added to the container and the contents of the container were stirred at about 20 °C for about 12 hours. The contents of the container were filtered and then concentrated under vacuum to obtain Example 1-1, which was observed to be a white solid (0.145 g, 98%). Example 1-1 can be further purified by extraction with a 1:1 hexane, toluene solution, followed by filtration, and concentration of the filtrate under vacuum. 1 H NMR (400 MHz, C6D6): δ 5.81 (q, J = 2.7 Hz, 4H), 5.65 (dt, J = 3.8, 2.7 Hz, 4H), 2.67 - 2.59 (m, 2H), 2.56 (d, J = 7.0 Hz, 2H), 1.62 (dp, J = 13.5, 6.7 Hz, 1H), 1.45 (h, J = 7.5 Hz, 2H), 0.83 (t, J = 7.4 Hz, 3H), 0.79 (d, J = 6.7 Hz, 6H). 13 C NMR (101 MHz, C6D6): δ 116.49, 115.52, 110.70, 110.62, 39.88, 32.47, 30.71, 24.41, 22.47, 14.03.

[0127] Examples 1-2, which are spray-dried compositions, were prepared as follows. In a nitrogen-purged glove box, hydrophobic fumed silica (CABOSIL TS-610, 0.665 grams) and toluene (19 grams) were added to a container, mixed, and then a 10 wt% solution of methylaluminoxane (MAO) in toluene (5.5 grams) was added. The contents of the container were stirred for about 15 hours. Then, Example 1-1 (0.024 grams) was added to the container, and the contents of the container were stirred for about 45 minutes. Then, the contents of the container were spray-dried using a Buchi Mini Spray Drier B-290 (set temperature of 185 °C, reaction temperature of 100 °C, pump speed of 150 rpm) to obtain Example 1-2.

[0128] The asymmetric metallocene, which is Example 2-1 and can be represented by the following formula:

[0129]

Chemical formula

[0130] Hafnium complex I (0.100 g, 246 mmol) and methylcyclopentadienyl lithium (0.021 g, 0.246 mmol) were added to a container. Then, Et2O was added to the container, and the contents of the container were stirred at about 20 °C for about 12 hours. The contents of the container were filtered and then concentrated under vacuum to obtain Example 2-1 (0.098 g, 88%). 1 H NMR (400 MHz, C6D6) δ 5.79 (t, J = 2.7 Hz, 2H), 5.75 - 5.70 (m, 1H), 5.62 (t, J = 2.7 Hz, 1H), 5.60 (t, J = 2.7 Hz, 1H), 2.54 (d, J = 7.0 Hz, 2H), 2.25 (d, J = 2.5 Hz, 1H), 2.18 (s, 3H), 1.60 (dq, J = 13.5, 6.7 Hz, 1H), 0.78 (d, J = 6.7 Hz, 6H).1 3 C NMR (101 MHz, C6D6) δ 116.43, 116.23, 110.71, 110.66, 39.86, 30.71, 22.46. <0,

[0131] Example 2-2, a spray-dried composition, was produced as follows. In a nitrogen-purged glove box, hydrophobic fumed silica (CABOSIL TS-610, 0.665 grams) and toluene (19 grams) were added to a container and mixed. Subsequently, a 10 wt% solution of methylaluminoxane (MAO) in toluene (5.5 grams) was added. The contents of the container were stirred for about 15 hours. Then, Example 2-1 (0.022 grams) was added to the container, and the contents of the container were stirred for about 45 minutes. Then, the contents of the container were spray-dried using a Buchi Mini Spray Drier B-290 (set temperature of 185°C, reaction temperature of 100°C, pump speed of 150 rpm) to obtain Example 2-2.

[0132] A hafnium metallocene having the same ligand as Comparative Example A-1 was produced as follows. Bis-(n-propylcyclopentadienyl)-hafnium dichloride was commercially obtained from TCI. This can be easily converted by those skilled in the art to bis-(n-propylcyclopentadienyl)hafnium dimethyl by reaction with a methylating agent such as a Grignard reagent such as methylmagnesium bromide.

[0133] Comparative Example A-1 can be represented by the following formula.

[0134]

Chemical formula

[0135] Comparative Example A-2, which is a spray-dried composition, was produced as follows. In a nitrogen-purged glove box, hydrophobic fumed silica (CABOSIL TS-610, 2.65 grams) and toluene (75.0 grams) were added to a container, mixed, and then a 10 wt% solution of methylaluminoxane (MAO) in toluene (22 grams) was added. The contents of the container were stirred for about 15 hours. Next, Comparative Example A-1 (0.110 grams) was added to the container, and the contents of the container were stirred for about 45 minutes. Then, the contents of the container were spray-dried using a Buchi Mini Spray Drier B-290 (set temperature of 185°C, reaction temperature of 100°C, pump speed of 150 rpm) to obtain Comparative Example A-2.

[0136] Example 3-1 is an example without supporting data of an asymmetric metallocene that can be represented by the following formula.

[0137] [Chemical formula]

[0138] In one or more embodiments, in Example 3-1, it is defined that X is Cl.

[0139] 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. Then, 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. When a steady state was reached, the catalyst was charged into the reactor (at the temperature shown below) to initiate 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 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 6.

[0140] For the polymers prepared in Example 1-2, Example 2-2, Example 4-2, Example 5-2, Example 6-2, and Comparative Example A-2, several properties were measured and the results are reported in Tables 1 to 6. Catalyst productivity (polymer (grams) / catalyst (grams)-hour) was determined as the ratio of the produced polymer 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 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 w were 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. The molecular weight comonomer distribution index (MWCDI) was determined as discussed herein.

[0141]

Table 2

[0142] The data in Table 1 show that the polymers produced in Example 1-2 and Example 2-2, respectively, had an improved, i.e., larger molecular weight comonomer distribution index (MWCDI), compared to the polymer produced in Comparative Example A-2.

[0143] Figure 1A shows data plots used to determine the MWCDI for Examples 1-2 (MWCDI = 5.85) and Comparative Example A-2 (MWCDI = 3.60), 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.

[0144]

Table 3

[0145] The data in Table 2 show that the polymers produced in Examples 1-2 and 2-2, respectively, had an improved, i.e., larger molecular weight comonomer distribution index (MWCDI), compared to the polymer produced in Comparative Example A-2.

[0146] Figure 1B shows data plots used to determine the MWCDI for Example 1-2 (MWCDI = 2.13) and Comparative Example A-2 (MWCDI = 1.67), as shown in Table 2. Data plot 106 corresponds to the determination of the MWCDI for Example 1-2. Data plot 106 corresponds to the determination of the MWCDI for Comparative Example A-2.

[0147] The asymmetric metallocene that can be represented by the following formula, which is Example 4-1:

Chemical formula

[0148] 1 H NMR (400 MHz, benzene-d6) δ 5.88 (t, J = 2.56 Hz, 2H), 5.81 (t, J = 2.68 Hz, 2H), 5.70 (t, J = 2.83 Hz, 2H), 5.67 (t, J = 2.83 Hz, 2H), 2.52 (d, J = 7.10 Hz, 2H), 2.13 (s, 3H), 1.61 (tq, 1H), 0.78 (d, J = 6.72 Hz, 6H).

[0149] The spray-dried composition, which is Example 4-2, was produced as follows. Inside a nitrogen-purged glove box, Cabosil TS-610 hydrophobic fumed silica (1.38 g) was slurried in toluene (36 g) until it was sufficiently dispersed. Then, a 10 wt% solution of MAO in toluene (11 g) was added and stirred for 15 minutes. Then, Example 4-1 (0.030 g) was added and stirred for 30 - 60 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 was spray-dried to obtain Example 4-2.

[0150] The asymmetric metallocene, which is Example 5-1, can be represented by the following formula:

[0151] [Chemical formula] was synthesized as follows. A solution of iso-butylcyclopentadienyllithium (0.09 g, 0.57 mmol) in THF (5 mL) was slowly added to a vial containing a solution of (methylcyclopentadienyl) zirconium trichloride (0.2 g, 0.59 mmol) in THF (5 mL), and the mixture was stirred at room temperature for about 12 hours. Then, the solvent was removed by vacuum, the residue was redissolved in toluene (10 mL), and filtered through a syringe filter. Then, the solution was concentrated to about 2 mL under vacuum, and pentane (10 mL) was added, forming a white precipitate. The solid was collected, washed with pentane (2 × 5 mL), and dried under vacuum to obtain Example 5-1 (0.13 g, 58%).

[0152] 1 H NMR (400 MHz, benzene-d6) δ 5.87 (m, 4H), 5.70 (m, 4H), 2.61 (q, 2H), 2.52 (d, J = 7.10 Hz, 2H), 1.61 (tq, 1H), 1.04 (t, J = 7.36 Hz, 3H), 0.78 (d, J = 6.66 Hz, 6H).

[0153] The spray-dried composition, which is Example 5-2, was produced as follows. Inside a nitrogen-purged glove box, Cabosil TS-610 hydrophobic fumed silica (1.32 g) was slurried in toluene (34 g) until it was sufficiently dispersed. Then, a 10 wt% solution of MAO in toluene (10.5 g) was added and stirred for 15 minutes. Then, Example 5-1 (0.030 g) was added and stirred for 30 - 60 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 was spray-dried to obtain Example 5-2.

[0154] The asymmetric mume metallocene, which is Example 6-1, can be represented by the following formula:

[0155] [Chemical formula] was synthesized as follows. A solution of iso-butylcyclopentadienyllithium (0.08 g, 0.57 mmol) in THF (5 mL) was slowly added to a vial containing a solution of (n-propylcyclopentadienyl)hafnium trichloride dimethoxyethane adduct (0.2 g, 0.57 mmol) in THF (5 mL), and the mixture was stirred at room temperature for about 12 hours. Then, the solvent was removed by vacuum, the residue was redissolved in toluene (10 mL), and filtered through a syringe filter. Then, the solution was concentrated to about 2 mL under vacuum, and pentane (10 mL) was added, forming a white precipitate. The solid was collected, washed with pentane (2 × 5 mL), and dried under vacuum to obtain Example 6-1 (0.20 g, 90%).

[0156] 1 H NMR (400 MHz, benzene-d6) δ 5.89 (m, 4H), 5.72 (m, 4H), 2.60 (t, J = 7.74 Hz, 2H), 2.54 (d, J = 6.97 Hz, 2H), 1.62 (septet, 1H), 1.45 (tq, 2H), 0.81 (t, J = 7.42 Hz, 3H), 0.79 (d, J = 6.58 Hz, 6H).

[0157] The spray-dried composition, Example 6-2, was prepared as follows. Inside a nitrogen-purged glove box, Cabosil TS-610 hydrophobic fumed silica (1.28 g) was slurried in toluene (33 g) until thoroughly dispersed. Then, a 10 wt% solution of MAO in toluene (10.2 g) was added and stirred for 15 minutes. Then, Example 6-1 (0.030 g) was added and stirred for 30 - 60 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 was spray-dried to obtain Example 6-2.

[0158] [Table 4]

[0159] The data in Table 3 indicate that the polymers prepared in Examples 4-2, 5-2, and 6-2 each had an inverse comonomer distribution (MWCDI > 0).

[0160] [Table 5]

[0161] The data in Table 4 indicate that the polymers prepared in Examples 4-2, 5-2, and 6-2 each had an inverse comonomer distribution (MWCDI > 0).

[0162] [Table 6]

[0163] The data in Table 5 indicate that the polymers prepared in Examples 4-2, 5-2, and 6-2 each had an inverse comonomer distribution (MWCDI > 0).

[0164] [Table 7]

[0165] The data in Table 6 indicate that the polymers prepared in Examples 4-2, 5-2, and 6-2 each had an inverse comonomer distribution (MWCDI > 0).

Claims

1. An asymmetric metallocene represented by structure (I), 【Chemical 1】 In the formula, M is Hf or Zr, and R １ is (C １ ~C ３ ) alkyl, (C ４ ) alkyl excluding 2-methylpropyl, or (C ５ ) alkyl, each X is independently a leaving group, and the (C ４ ) alkyl excluding 2-methylpropyl is selected from butyl, 1-methylpropyl, and 1,1-dimethylethyl, an asymmetric metallocene.

2. where M is Hf and the asymmetric metallocene is represented by structure (Ia), [Chemical 2] wherein R １ is as defined in claim 1, and each X is independently a leaving group selected from halogen, (C １ ~C ５ )alkyl, CH ２ SiMe ３ , and benzyl, the asymmetric metallocene according to claim 1.

3. where M is Zr and the asymmetric metallocene is represented by structure (Ib), 【Chemical 3】 wherein R １ is as defined in claim 1, and each X is independently a leaving group selected from halogen, (C １ ~C ５ )alkyl, CH ２ SiMe ３ , and benzyl, the asymmetric metallocene according to claim 1.

4. R １ is the above (C １ -C ３ ) alkyl, and the above (C １ -C ３ ) alkyl is (C ３ ) alkyl, ethyl or methyl, and the above (C ３ ) alkyl is selected from 1-methylethyl and n-propyl, or R １ is the above (C ４ ) alkyl that is not 2-methylpropyl, or R １ is the above (C ５ ) alkyl, the asymmetric metallocene according to any one of claims 1 to 3.

5. each X is Cl or each X is CH ３ The asymmetric metallocene according to any one of claims 1 to 4.

6. A hafnium asymmetric metallocene represented by structures (II) to (IV): 【Chemical Formula 4】 or a zirconium asymmetric metallocene represented by structures (V) to (VII): 【Chemical Formula 5】 selected from the group consisting of, In Structures (II) to (VII), each X is Cl or each X is CH ３ The asymmetric metallocene according to claim 1, wherein is

7. A method for synthesizing the asymmetric metallocene according to any one of Claims 1 to 6, wherein each X is Cl, and the method is for producing the asymmetric metallocene, a hafnium complex or a zirconium complex is contacted with an alkali metal complex, and the alkali metal complex has the following structure: [Chemical Formula 6] (wherein M' is lithium, sodium, or potassium) represented by, the hafnium complex or the zirconium complex has one of the following structures: 【Chemical Formula 7】 (wherein M is Hf or Zr, respectively, and R １ is as defined in the above claims), contacting with an alkali metal complex, or a hafnium complex or a zirconium complex is contacted with an alkali metal complex, and the alkali metal complex has the following structure: 【Chemical Formula 8】 (wherein, M' is lithium, sodium, or potassium, and R １ is as defined in the above claims) and is represented by the hafnium complex or the zirconium complex has one of the following structures: 【Chemical Formula 9】 (wherein M is Hf or Zr, respectively) represented by, the method comprising contacting with an alkali metal complex.

8. Contact the asymmetric metallocene 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 the asymmetric metallocene of structure (I) (wherein each X is (C １ ~C ５ ) alkyl, CH ２ SiMe ３ , or benzyl), the method according to claim 7.

9. A metallocene catalyst composition comprising, the asymmetric metallocene according to any one of Claims 1 to 6, or the asymmetric metallocene produced by the method according to Claim 7 or Claim 8, and an activator. The metallocene catalyst composition.

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

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

12. A method for producing the metallocene catalyst composition according to any one of claims 9 to 11, wherein the method comprises contacting the asymmetric metallocene with the activator rather than the carrier to obtain the metallocene catalyst composition according to claim 9 without a carrier, or contacting the asymmetric metallocene with the activator and the carrier to obtain the metallocene catalyst composition according to claim 10 having the 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 the spray-dried metallocene catalyst composition according to claim 11, 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 according to claim 11, the method comprising any one of these.

13. A method for producing a polyolefin polymer, At least one olefin monomer is polymerized with any of the metallocene catalyst compositions according to any one of claims 9 to 11, or the metallocene catalyst composition produced by the method according to claim 12, 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, a method.

14. 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 13.

15. A polyolefin polymer produced by the method according to claim 13 or 14.

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