Asymmetric metallocenes with isobutylcyclopentadienyl ligands

Abstract

Embodiments of the present disclosure relate to asymmetric metallocenes having isobutyl cyclopentadienyl ligands, compositions comprising those asymmetric metallocenes, and methods of utilizing compositions comprising asymmetric metallocenes.

Description

Technical Field

[0001] Embodiments of the present disclosure relate to asymmetric metallocenes, catalyst compositions comprising the same, methods of making and using the same, and polyolefins made therefrom. Background Art

[0002] Metallocenes can be used in a variety of applications, including as polymerization catalysts. Polymers can be used in a variety of products, including membranes, etc. Polymers can be formed by reacting one or more types of monomers in a polymerization reaction. The industry is constantly working to develop new and improved materials and / or methods that can be used to form polymers. Summary of the invention

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

[0004] An asymmetric metallocene represented by structure (I):

[0005]

[0006] Where: M is Hf or Zr; R 1 Yes (C 1 -C 3 ) alkyl, except 2-methylpropyl (C 4 ) alkyl, or (C 5 ) alkyl; and each X is independently a leaving group; wherein (C 4 ) The alkyl group is selected from butyl, 1-methylpropyl and 1,1-dimethylethyl.

[0007] An asymmetric metallocene catalyst composition comprises an asymmetric metallocene and an activator.

[0008] A method for preparing an asymmetric metallocene catalyst composition comprises contacting an asymmetric metallocene with an activator.

[0009] A method for preparing a polyolefin polymer comprises polymerizing at least one olefin monomer with an asymmetric metallocene catalyst composition to prepare the polyolefin polymer. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1A and Figure 1B Shown is a graph of data for determining the molecular weight comonomer distribution index (MWCDI) according to various embodiments of the present disclosure. DETAILED DESCRIPTION

[0011] Asymmetric metallocenes with isobutylcyclopentadienyl ligands are discussed herein. Advantageously, these asymmetric metallocenes can be used to prepare, for example, catalyst compositions. These catalyst compositions can be used to prepare such polymers, which have improved (i.e., larger) molecular weight comonomer distribution indexes (MWCDI) compared to other polymers prepared by other metallocenes. These polymers are desired by many applications (including films, etc.). Therefore, it is advantageous to provide improved MWCDI. Such polymers are advantageous for many applications.

[0012] An asymmetric metallocene having an isobutylcyclopentadienyl ligand and can be represented by structure (I):

[0013]

[0014] Where: M is Hf or Zr; R 1 Yes (C 1 -C 3 ) alkyl, except 2-methylpropyl (C 4 ) alkyl, or (C 5 ) alkyl; and each X is independently a leaving group; wherein (C 4 ) alkyl is selected from butyl, 1-methylpropyl and 1,1-dimethylethyl. As shown in structure (I), the upper cyclopentadienyl ring is surrounded by a monovalent structure -CH 2 CH(CH 3 ) 2 The isobutyl group (also known as the 2-methylpropyl group) is substituted.

[0015] One or more embodiments of the present disclosure provide that M is Hf. One or more embodiments of the present disclosure provide that M is Zr.

[0016] For example, one or more embodiments provide that M is Hf and the asymmetric metallocene is represented by structure (Ia):

[0017]

[0018] Where: R 1 Yes (C 1 -C 3 ) alkyl, except 2-methylpropyl (C 4 ) alkyl, or (C 5 ) alkyl; and each X is independently selected from halogen, (C 1 -C 5 ) alkyl, CH 2 SiMe 3 and a leaving group of benzyl. One or more embodiments provide that X is selected from Cl, (C 1 -C 3)alkyl, and benzyl. One or more embodiments provide that X is CH 3 .

[0019] One or more embodiments provide that M is Zr and the asymmetric metallocene is represented by structure (Ib):

[0020]

[0021] Where: R 1 Yes (C 1 -C 3 ) alkyl, except 2-methylpropyl (C 4 ) alkyl, or (C 5 ) alkyl; and each X is independently selected from halogen, (C 1 -C 5 ) alkyl, CH 2 SiMe 3 and a leaving group of benzyl. One or more embodiments provide that X is selected from Cl, (C 1 -C 3 )alkyl, and benzyl. One or more embodiments provide that X is CH 3 .

[0022] One or more embodiments of the present disclosure provide that the ligand having the cyclopentadienyl ring of the isobutylcyclopentadienyl ligand shown in structure (I) is different from the ligand comprising R 1 Thus, the asymmetric metallocenes discussed herein may be referred to as having different ligands. As an example, the embodiments provide that R 1 Not isobutyl.

[0023] One or more embodiments provide that R 1 Yes (C 1 -C 3 ) alkyl, except 2-methylpropyl (C 4 ) alkyl, or (C 5 ) alkyl. One or more embodiments provide that: R 1 Yes (C 5 ) alkyl. One or more embodiments provide that R 1 Except 2-methylpropyl 4 ) alkyl. One or more embodiments provide that R 1 Yes (C 1 -C 3 ) alkyl. One or more embodiments provide that R 1 Yes (C 1 -C 2 ) alkyl. One or more embodiments provide that R 1 Yes (C 3 ) alkyl. (C3 ) The alkyl group may be branched or straight chain. As used herein, "Pr" and "n-Pr" refer to CH 2 CH 2 CH 3 One or more embodiments of the present disclosure provide that R 1 Yes (C 2 ) alkyl. One or more embodiments of the present disclosure provide that R 1 Yes (C 2 ) alkyl. One or more embodiments of the present disclosure provide that R 1 For (C 3 ) alkyl, ethyl, or methyl. 3 ) The alkyl group is selected from 1-methylethyl and propyl.

[0024] 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 chlorine. One or more embodiments provide that X is methyl. One or more embodiments provide that X is selected from halogen, (C 1 -C 5 ) alkyl, CH 2 SiMe 3 and benzyl.

[0025] Examples of X include halogen ions, hydrides, (C 1 To C 12 ) alkyl, (C 2 To C 12 ) alkenyl, (C 6 To C 12 ) aryl, (C 7 To C 20 ) alkylaryl, (C 1 To C 12 ) alkoxy, (C 6 To C 16 ) aryloxy, (C 7 To C 8 ) alkylaryloxy, (C 1 To C 12 ) fluoroalkyl, (C 6 To C 12 ) fluoroalkyl and (C 1 To C 12 ) heteroatom-containing hydrocarbons and their substituted derivatives; one or more embodiments include hydrides, halides, (C 1 To C 6 ) alkyl, (C 2 To C 6 ) alkenyl, (C 7 To C18 ) alkylaryl, (C 1 To C 6 ) alkoxy, (C 6 To C 14 ) aryloxy, (C 7 To C 16 ) alkylaryloxy, (C 1 To C 6 ) alkyl carboxylate, (C 1 To C 6 ) fluorinated alkyl carboxylate, (C 6 To C 12 ) aryl carboxylate, (C 7 To C 18 ) alkyl aryl carboxylate, (C 1 To C 6 ) fluoroalkyl, (C 2 To C 6 ) fluoroalkenyl and (C 7 To C 18 ) fluoroalkylaryl; one or more embodiments include hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoyloxy, tosyl, fluoromethyl and fluorophenyl; one or more embodiments include (C 1 To C 12 ) alkyl, (C 2 To C 12 ) alkenyl, (C 6 To C 12 ) aryl, (C 7 To C 20 ) alkylaryl, substituted (C 1 To C 12 ) alkyl, substituted (C 6 To C 12 ) aryl, substituted (C 7 To C 20 ) alkylaryl and (C 1 To C 12 ) containing heteroatom alkyl, (C 1 To C 12 ) containing heteroatom aromatic groups and (C 1 To C 12 ) containing heteroatom alkylaryl; one or more embodiments include chloride, fluoride, (C 1 To C 6 ) alkyl, (C 2 To C 6 ) alkenyl, (C 7 To C 18 ) alkylaryl, halogenated (C 1 To C 6 ) alkyl, halogenated (C 2 To C6 )alkenyl and halogenated (C 7 To C 18 ) alkylaryl; one or more embodiments include fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyl (monofluoromethyl, difluoromethyl and trifluoromethyl) and fluorophenyl (monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl and pentafluorophenyl).

[0026] Other non-limiting examples of X groups include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon groups having 1 to 20 carbon atoms, fluorinated hydrocarbon groups (e.g., -C 6 F 5 (pentafluorophenyl)), fluorinated alkyl carboxylates (e.g., CF 3 C(O)O-), hydrides, halides, and combinations thereof. Other examples of X ligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylene, methoxy, ethoxy, propoxy, phenoxy, bis(N-methylaniline), dimethylamido, and dimethylphosphoryl, among others. In one embodiment, two or more X form a fused ring or part of a ring system. In one or more embodiments, X can be a leaving group selected from the group consisting of chloride, bromide, (C(O)O-), halides, and combinations thereof. 1 To C 10 ) alkyl, (C 2 To C 12 ) alkenyl, carboxylate, acetylacetonate, and alcoholate. In one or more embodiments, X is methyl.

[0027] The asymmetric metallocenes discussed herein can be prepared by contacting a Hf complex or a Zr complex with an alkali metal complex to prepare an asymmetric metallocene. For example, the alkali metal complex can be a lithium complex, such as isobutyl-butylcyclopentadienyl lithium, methylcyclopentadienyl lithium, ethylcyclopentadienyl lithium, n-propylcyclopentadienyl lithium, etc. The asymmetric metallocenes discussed herein can be prepared by methods for preparing known metallocenes (e.g., using conventional solvents, reaction conditions, reaction times, and separation procedures).

[0028] The alkali metal complex can be represented by the following structure:

[0029]

[0030] Wherein M' is lithium, sodium or potassium.

[0031] One or more embodiments provide that the hafnium complex or the zirconium complex may be represented by the following structure:

[0032]

[0033] Where M is Hf or Zr, and R 1 As defined herein (e.g., R 1 is propyl).

[0034] One or more embodiments provide that the hafnium complex or the zirconium complex may be represented by the following structure:

[0035]

[0036] Where M is Hf or Zr, and R 1 As defined herein (e.g., R 1 is propyl).

[0037] The alkali metal complex can be represented by the following structure:

[0038]

[0039] Where M' is lithium, sodium or potassium, and R 1 As defined herein (e.g., R 1 is propyl).

[0040] One or more embodiments provide that the hafnium complex or the zirconium complex may be represented by the following structure:

[0041]

[0042] Wherein M is Hf or Zr respectively.

[0043] One or more embodiments provide that the hafnium complex or the zirconium complex may be represented by the following structure:

[0044]

[0045] Wherein M is Hf or Zr respectively.

[0046] One or more embodiments provide a method for preparing an asymmetric metallocene (e.g., wherein each X is Cl) comprising: reacting the asymmetric metallocene with two molar equivalents of an organomagnesium halide of the formula RMg(halide) or one molar equivalent of R 2 Mg contact, where R is (C 1 -C 5 ) alkyl, CH 2 SiMe 3 or benzyl; and the halide is Cl or Br, to prepare an asymmetric metallocene of structure (I), wherein each X is (C 1 -C 5 ) alkyl, CH 2 SiMe 3 or benzyl. One or more embodiments provide that X is CH3 .

[0047] As used herein, all references to the Periodic Table of the Elements and its Groups refer to the NEW NOTATION as published in HAWLEY'S CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition, John Wiley & Sons, Inc. (1997) (reproduced with permission from IUPAC), unless reference is made to the previous IUPAC form marked with Roman numbering (which also appears therein) or unless otherwise mentioned.

[0048] As used herein, "alkyl" includes straight chain, branched chain, and cyclic alkane groups lacking one hydrogen. Thus, for example, CH 3 ("methyl") and CH 2 CH 3 ("ethyl") is an example of an alkyl group.

[0049] As used herein, "alkenyl" includes straight chain, branched chain, and cyclic alkene groups lacking one hydrogen group; alkynyl includes straight chain, branched chain, and cyclic ethynyl groups lacking one hydrogen group.

[0050] As used herein, "aryl" groups include phenyl, naphthyl, pyridyl and other groups whose molecules have the ring structure characteristics of benzene, naphthylene, phenanthrene, anthracene, etc. It should be understood that "aryl" groups can be C 6 To C 20 Aryl groups. For example, C 6 H 5 The aromatic structure is "phenyl", C 6 H 4 2 aromatic structure is a "phenylene". An "aralkyl" group is an alkyl group with a pendant aryl group. It is understood that an "aralkyl" group can be (C 7 To C 20 ) aralkyl groups. "Alkaryl" is an aryl group having one or more pendant alkyl groups.

[0051] As used herein, "alkylene" includes straight chain, branched chain, and cyclic hydrocarbon groups lacking two hydrogen atoms. 2 ("methylene") and CH 2 CH 2 ("Ethylene") is an example of an alkylene group. Other groups lacking two hydrogen radicals include "arylene" and "alkenylene".

[0052] 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 heteroatoms and may contain one or more heteroatoms of the same heteroatom or different heteroatoms, and may contain 1 to 3 heteroatoms in a specific embodiment. Non-limiting examples of heteroatom-containing groups include groups (monovalent and divalent groups) of imines, amines, oxides, phosphines, ethers, ketones, oxazoline heterocycles, oxazolines and thioethers.

[0053] As used herein, the term "substituted" means that one or more hydrogen atoms in the parent structure have been independently replaced with a substituent atom or group.

[0054] The asymmetric metallocenes discussed herein can be used to prepare catalyst compositions. These asymmetric metallocene compositions include: an asymmetric metallocene with 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 supported or unsupported compound or combination of compounds, which can, for example, activate the complex or catalyst component by generating a cationic species of the catalyst component. For example, this can include capturing at least one leaving group, for example, the "X" group described herein, from the metal center of the complex / catalyst component (e.g., the asymmetric metallocene of structure (I)). The activator may also be referred to as a "co-catalyst". As used herein, "leaving group" refers to one or more chemical moieties that are bound to a metal atom and can be captured by an activator, thereby generating a substance 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 can be used. Different amounts of known catalyst composition components can be used for different applications.

[0055] The asymmetric metallocenes discussed herein can be used to prepare spray-dried compositions. As used herein, a "spray-dried composition" refers to a composition comprising a number of components that has undergone a spray-drying process. Various spray-drying processes are known in the art and are suitable for forming the spray-dried compositions disclosed herein. One or more embodiments provide that the spray-dried composition comprises a conditioning composition.

[0056] In one or more embodiments, the spray drying process may include atomizing a composition comprising an asymmetric metallocene with an isobutylcyclopentadienyl ligand. Many other known components may be used in the spray drying process. Atomizers such as atomizing nozzles or centrifugal high-speed disks may be used, for example, to produce a spray or dispersion of composition droplets. The droplets of the composition may then be rapidly dried by contact with an inert dry gas. An inert dry gas may be any gas that is not reactive under the conditions employed during atomization, such as nitrogen. An inert dry gas may encounter the composition at the atomizer, which produces a droplet stream on a continuous basis. The dried composition particles may be captured from the process in a separator such as a cyclone separator, which may separate the solid formed from a gas mixture of a dry gas, a solvent, and other volatile components.

[0057] For example, the spray-dried composition can have a free-flowing powder form. After the spray-drying process, the spray-dried composition and many known components can be used to form a slurry. The spray-dried composition can be used together with a diluent to form a slurry suitable for, for example, olefin polymerization. In one or more embodiments, the slurry can be combined with one or more additional catalysts or other known components before being delivered to a polymerization reactor.

[0058] In one or more embodiments, a spray-dried composition can be formed by contacting spray-dried activator particles (such as spray-dried MAO) with a solution of an asymmetric metallocene having an isobutylcyclopentadienyl ligand. Such solutions can typically be prepared in, for example, an inert hydrocarbon solvent and are sometimes referred to as a conditioning solution. Such spray-dried compositions comprising contacting a conditioning solution of an asymmetric metallocene with spray-dried activator particles (such as spray-dried MAO) can be prepared in situ in a feed conduit to a gas phase polymerization reactor by contacting the conditioning solution with a slurry of spray-dried activator particles (usually in mineral oil).

[0059] Various spray drying conditions can be used for different applications. For example, the spray drying process can utilize a drying temperature of 75° C. to 185° C. Other drying temperatures are also possible, wherein the temperature can depend on the metallocene and the activator. Various sizes of the orifice of the atomizing nozzle used during the spray drying process can be used to obtain different sizes. Alternatively, for other types of atomizers such as disks, the speed, disk size, and number / size of holes can be adjusted to obtain different sizes. One or more embodiments provide that fillers can be used in the spray drying process. Different fillers and their amounts can be used for various applications.

[0060] The asymmetric metallocenes discussed herein (e.g., catalyst compositions, such as spray-dried asymmetric metallocene compositions) can be used to prepare polymers. For example, the asymmetric metallocene can be activated (i.e., with an activator) to prepare an asymmetric metallocene catalyst. 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, which can activate the complex or catalyst component, such as by generating a cationic species of the catalyst component, for example to provide a catalyst. The activator may also be referred to as a "cocatalyst". The activator may include a Lewis acid or a non-coordinating ion activator or an ionizing activator, or any other compound including a Lewis base, an alkyl aluminum and / or a conventional cocatalyst. The activator includes methylaluminoxane (MAO) and modified methylaluminoxane (MMAO), etc. One or more embodiments provide that the activator is methylaluminoxane. Activation conditions are well known in the art. Known activation conditions can be used.

[0061] The molar ratio of the metal (e.g., aluminum) in the activator to the Hf or Zr in the asymmetric metallocene with an isobutylcyclopentadienyl ligand can be 1500: 1 to 0.5: 1, 300: 1 to 1: 1, or 150: 1 to 1: 1. One or more embodiments provide that the molar ratio of the activator to the Hf or Zr in the asymmetric metallocene is at least 75: 1. One or more embodiments provide that the molar ratio of the activator to the Hf or Zr in the asymmetric metallocene is at least 100: 1. One or more embodiments provide that the molar ratio of the activator to the Hf or Zr in the asymmetric metallocene is at least 150: 1.

[0062] Asymmetric metallocenes with isobutylcyclopentadienyl ligands and many other components discussed herein can be loaded on the same or independent carriers, or one or more of these components can be used in a non-loaded form. The use of the carrier can be achieved by any technology used in the art. One or more embodiments provide that a spray drying process is utilized. The carrier can be functionalized. One or more embodiments provide that the spray-dried composition comprises a carrier.

[0063] "Carrier" may also be referred to as "support", and refers to any carrier material, including porous carrier materials (such as talc), inorganic oxides and inorganic chlorides. Other carrier materials include resin carrier materials (e.g., polystyrene), functionalized or cross-linked organic carriers (such as polystyrene divinyl benzene polyolefins or polymeric compounds), zeolites, clays or any other organic or inorganic carrier materials, etc., or mixtures thereof.

[0064] The support material includes an inorganic oxide including a Group 2, 3, 4, 5, 13 or 14 metal oxide. Some preferred supports include silica, fumed silica, alumina, silica-alumina and mixtures thereof. Some other supports include magnesium oxide, titanium dioxide, zirconium oxide, magnesium chloride, montmorillonite, phyllosilicates, zeolites, talc, clays and the like. Moreover, combinations of these support materials may be used, such as silica-chromium, silica-alumina, silica-titania and the like. One or more embodiments provide that the support is a hydrophobic pyrogenic silica. Additional support materials may include porous acrylic polymers, nanocomposites, aerogels, spherulites and polymer beads. An example of a support is available under the trade name Cabosil TM Fumed silica obtained from TS-610, or other TS-series or TG-series supports available from Cabot Corporation. Fumed silica is typically silica having a particle size of 7 to 30 nanometers that has been treated with dimethylsilyl dichloride such that most of the surface hydroxyl groups are capped.

[0065] The asymmetric metallocene discussed herein (e.g., a catalyst composition / spray-dried asymmetric metallocene composition) and an olefin can be contacted under polymerization conditions to prepare a polymer, e.g., a polyolefin polymer. The polymerization process can be a solution polymerization process, a suspension polymerization process, a slurry polymerization process, and / or a gas phase polymerization process. The polymerization process can utilize known equipment and reaction conditions, e.g., known polymerization conditions. The polymerization process is not limited to any particular type of polymerization system. The polymer can be used in many articles, such as films, fibers, nonwoven fabrics and / or woven fabrics, extruded articles, and / or molded articles.

[0066] One or more embodiments provide for the use of a gas phase reactor system to prepare the polymer. One or more embodiments provide for the use of a single gas phase reactor, for example, as opposed to a series of reactors. In other words, the polymerization reaction occurs in only one reactor. For example, a fluidized bed reactor may be used to prepare the polymer. Gas phase reactors are known, and known components can be used in fluidized bed reactors.

[0067] As used herein, "olefins" which may be referred to as "alkenes" refer to linear, branched or cyclic compounds including carbon and hydrogen and having at least one double bond. As used herein, when polyolefins, polymers and / or copolymers are referred to as comprising olefins (e.g., prepared by olefins), the olefins present in such polymers or copolymers are olefins in polymerized form. For example, when it is said that the ethylene content of the copolymer is 75% to 95% by weight, it is understood that the polymer units in the copolymer are derived from ethylene in the polymerization reaction, and based on the gross weight of the polymer, the derived units are present in 75% to 95% by weight. High-grade alpha-olefins refer to alpha-olefins with 3 or more carbon atoms.

[0068] The polyolefins prepared with the compositions discussed herein can be prepared from olefin monomers, such as ethylene (i.e., polyethylene) or propylene (i.e., polypropylene), and other substances specified herein, wherein the polyolefin is a homopolymer prepared only from olefin monomers (e.g., prepared from 100% by weight ethylene or 100% by weight propylene). Alternatively, the polyolefins prepared with the compositions discussed herein can be prepared from olefin monomers, such as ethylene (i.e., polyethylene), and straight 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 ethylene-based polymers having at least 50% by weight ethylene, including ethylene-1-butene, ethylene-1-hexene, and ethylene-1-octene copolymers, etc. One or more embodiments provide that, based on the total weight of the polymer, the polymer may include 50% by weight to 99.9% by weight of units derived from ethylene. All individual values ​​and subranges from 50 wt % to 99.9 wt % are included; for example, based on the total weight of the polymer, the polymer may include a lower limit of 50 wt %, 60 wt %, 70 wt %, 80 wt % or 90 wt % of units derived from ethylene to an upper limit of 99.9 wt %, 99.7 wt %, 99.4 wt %, 99 wt %, 96 wt %, 93 wt %, 90 wt % or 85 wt % of units derived from ethylene. Based on the total weight of the polymer, the polymer may include 0.1 wt % to 50 wt % of units derived from comonomers. One or more embodiments provide that ethylene is used as a monomer and hexene is used as a comonomer.

[0069] As mentioned, polymers prepared using the compositions disclosed herein can be prepared in a fluidized bed reactor. The fluidized bed reactor can have a reaction temperature of 10°C to 130°C. All individual values ​​and subranges from 10°C to 130°C are included; for example, the fluidized bed reactor can have a reaction temperature of 10°C, 20°C, 30°C, 40°C, 50°C, or 55°C at a lower limit to 130°C, 120°C, 110°C, 100°C, 90°C, 80°C, 70°C, or 60°C at an upper limit.

[0070] The fluidized bed reactor can have an ethylene partial pressure of 30 pounds per square inch (psi) to 250 psi, including all individual values ​​and subranges from 30 to 250; for example, the fluidized bed reactor can have an ethylene partial pressure of 30 psi, 45 psi, 60 psi, 75 psi, 85 psi, 90 psi, or 95 psi on the lower limit and 250 psi, 240 psi, 220 psi, 200 psi, 150 psi, or 125 psi on the upper limit.

[0071] One or more embodiments provide for using ethylene as the monomer and hexene as the comonomer. The fluidized bed reactor may have a comonomer to ethylene molar ratio of 0.0001 to 0.100, for example, C 6 / C 2 All individual values ​​and subranges from 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.

[0072] When hydrogen is used in the polymerization process, the fluidized bed reactor may have a hydrogen to ethylene molar ratio (H ) of, for example, 0.00001 to 0.90000. 2 / C 2 ). All individual values ​​and subranges from 0.00001 to 0.90000 are included; for example, a fluidized bed reactor may have a H with a lower limit of 0.00001, 0.00005, or 0.00008 and an upper limit of 0.90000, 0.500000, 0.10000, 0.01500, 0.00700, or 0.00500. 2 / C 2 One or more embodiments provide that hydrogen is not utilized.

[0073] Conventional gel permeation chromatography can be used to determine multiple polymer properties. For example, a chromatographic system consisting of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) is used to determine weight average molecular weight (Mw), number average molecular weight (Mn), Z average molecular weight (Mz) and Mw / Mn (PDI). The autosampler oven chamber is set to 160°C, and the column chamber is set to 150°C. The column used is 4 Agilent "MixedA" 30cm 20 micron linear mixed bed columns. The chromatographic solvent used is 1,2,4 trichlorobenzene and contains 200ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0074] Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards ranging from 580 g / mol to 8,400,000 g / mol and arranged in 6 "cocktail" mixtures with at least ten times intervals between individual molecular weights. Standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g of polystyrene standards were prepared in 50 ml of solvent, and for molecular weights less than 1,000,000, 0.05 g of polystyrene standards were prepared in 50 ml of solvent. The polystyrene standards were pre-dissolved at 80°C with gentle stirring for 30 minutes, then cooled and the room temperature solution transferred to a 160°C autosampler dissolution oven to cool for 30 minutes. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

[0075] M 聚乙烯 =A×(M 聚苯乙烯 ) B (Equation 1) where M is the molecular weight, A has a value of 0.4061, and B is equal to 1.0.

[0076] A fifth-order polynomial was used to fit the calibration points to the corresponding polyethylene equivalents.

[0077] Total plate counts for the GPC column set were performed with decane, which was introduced into the blank sample via a micro pump controlled by the PolymerChar GPC-IR system. The plate count of the chromatography system should be greater than 18,000 for 4 Agilent "Mixed A" 30 cm 20 micron linear mixed bed columns.

[0078] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the sample was set at 2 mg / ml and the solvent (containing 200 ppm BHT) was added to a septum-capped vial previously sparged with nitrogen via the PolymerChar high temperature autosampler. The samples were dissolved at 160°C for 2 hours under "low speed" shaking.

[0079] Mn was determined based on GPC results using the internal IR5 detector (measurement channel) of a PolymerChar GPC-IR spectrometer according to Equations 2-4 using the PolymerChar GPCONE software, the baseline-subtracted IR chromatogram at each equally spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) 、Mw (GPC) and Mz (GPC) Calculation:

[0080]

[0081]

[0082] To monitor the deviation over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly calibrate the pump flow rate (flow rate) for each sample by the following method: (标称) ): The RV of the corresponding decane peak in the sample (RV (FM样品) ) and the retention volume (RV (FM校准) ). It is then assumed that any changes in the decane marker peak time are related to the flow rate (flow rate) during the entire run. (有效) ). After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) is calculated according to Equation 5. Processing of the flow marker peak is completed by PolymerChar GPCONE software. An acceptable flow rate correction is such that the effective flow rate should be within + / - 0.5% of the nominal flow rate.

[0083] Flow rate (effective) = flow rate (nominal) × (RV (FM calibration) / RV (FM sample)) (Equation 5)

[0084] IR5 GPC Octene Composition Calibration. Calibration for IR5 detector dosing is performed using at least ten ethylene-based polymer standards (octene as comonomer) produced in a solution process (polyethylene homopolymer and ethylene / octene copolymer) from a single reactor over a single site metallocene catalyst with narrow SCB distribution and known comonomer content (e.g., by 13 C NMR method, Qiu et al., Anal. Chem.) 2009, 81, 8585-8589) in a solution process (polyethylene homopolymer and ethylene / octene copolymer) from a single reactor by a single-site metallocene catalyst, the known monomer content is in the range of from homopolymer (0 SCB / 1000 total C) to about 40 SCB / 1000 total C, where total C = carbon in the main chain + carbon in the branch chain. Each standard has a weight average molecular weight of 36,000 g / mole to 126,000 g / mole, as measured by GPC. The molecular weight distribution (Mw / Mn) of each standard is 2.0 to 2.5. The SCB standard polymer properties are shown in Table A.

[0085] Table A: "Copolymer" Standards

[0086]

[0087]

[0088] The “IR5 Area Ratio” (or “IR5 Area Response”) of the “Baseline-Subtracted Area Response of the IR5 Methyl Channel Sensor” to the “Baseline-Subtracted Area Response of the IR5 Measurement Channel Sensor” was calculated for each of the “Copolymer” standards. 甲基通道面积 / IR5 测量通道面积 ”)” (including standard filters and filter wheels supplied by PolymerChar: Part No. IR5_FWM01 as part of the GPC-IR instrument). A linear fit of comonomer wt% frequency versus “IR5 Area Ratio” was constructed in the form of Equation 6 below:

[0089] Comonomer weight % = A 0 +[A 1 ×(IR5 甲基通道面积 / IR5 测量通道面积 )] (Equation 6)

[0090] Among them A 0 is the "comonomer weight %" intercept at the "IR5 area ratio" of zero, and A 1is the slope of "Comonomer wt%" versus "IR5 Area Ratio" and represents the increase in comonomer wt% as a function of "IR5 Area Ratio." For the narrow PDI and narrow SCBD standard materials, the IR5 Area Ratio is equal to the IR5 Height Ratio.

[0091] The comonomer distribution or short chain branching distribution in ethylene / α-olefin copolymers can be characterized as normal (also referred to as having a Ziegler-Natta distribution), inverse or flat. Several reported methods are used to quantify broad orthogonal composition distribution (BOCD). Herein, a simple straight line fit is used so that the normal 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 measured by composition GPC, where the x-axis is Log (MW), and the y-axis is the weight percent of the comonomer. Figure 1A Shown are graphs of data used to determine the MWCDI for Example 1-2 (MWCDI = 5.85) and for determining the MWCDI for Comparative Example A-2 (MWCDI = 3.60), as shown in Table 1 of the Examples section of the present application. Figure 1B Shown are graphs of data used to determine the MWCDI for Example 1-2 (MWCDI = 2.13) and for Comparative Example A-2 (MWCDI = 1.67), as shown in Table 2 of the Examples section of the present application.

[0092] The reverse 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. In addition, MWCDI quantifies the magnitude of the comonomer distribution. Comparing two polymers with MWCDI>0, the polymer with a 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 reverse comonomer distribution. For example, as reported in Tables 1 and 2, respectively, Examples 1-2, 2-2, and 3-2 each have an increased BOCD compared to Comparative Example A-2. Compared to polymers with relatively smaller MWCDI, polymers with relatively larger MWCDI (i.e., BOCD) can provide improved physical properties, such as improved film properties.

[0093] Polymers prepared with the compositions disclosed herein may have a 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 a 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 provide that the polymer may have a MWCDI of 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, as well as other ranges.

[0094] The polymers prepared using the compositions disclosed herein may have a hardness of 0.8700 g / cm 3 Up to 0.9700g / cm 3 Density. Including 0.8700g / cm 3 Up to 0.9700g / cm 3 All individual values ​​and subranges of; for example, a polymer may have a lower limit of 0.8700 g / cm 3 , 0.9000g / cm 3 、0.9100g / cm 3 、0.9150g / cm 3 , 0.9200g / cm 3 or 0.9250g / cm 3 The upper limit is 0.9700g / cm 3 , 0.9600g / cm 3 , 0.9500g / cm 3 、0.9450g / cm 3 、0.9350g / cm 3 or 0.9300g / cm 3 The density can be determined according to ASTM D792.

[0095] The polymers prepared using the compositions disclosed herein may have a melt index (I) of 0.0 dg / min to 10 dg / min. 2 ). It can be measured according to ASTM D1238 (190°C, 2.16kg). 2 . All individual values ​​and subranges from 1.0 dg / min to 10 dg / min are included; for example, a polymer can have an I with a lower limit of 0.0 dg / min, 0.05 dg / min, 0.07 dg / min, or 0.10 dg / min and an upper limit of 10 dg / min, 5 dg / min, or 3 dg / min. 2 .

[0096] The polymers prepared using the compositions disclosed herein may have a melt index (I) of 0.05 dg / min to 15 dg / min. 5 ). It can be measured according to ASTM D1238 (190°C, 5kg). 5 . All individual values ​​and subranges from 0.05 dg / min to 15 dg / min are included; for example, a polymer can have an I with a lower limit of 0.05 dg / min, 0.07 dg / min, or 0.10 dg / min and an upper limit of 15 dg / min, 10 dg / min, or 5 dg / min. 5 .

[0097] The polymers prepared using the compositions disclosed herein may have a melt index (MI) of 0.05 dg / min to 25 dg / min. 21 ). It can be measured according to ASTM D1238 (190°C, 21.6kg). 21 . All individual values ​​and subranges from 0.05 dg / min to 25 dg / min are included; for example, a polymer can have an I with a lower limit of 0.05 dg / min, 0.07 dg / min, or 0.10 dg / min and an upper limit of 25 dg / min, 15 dg / min, or 5 dg / min. 21 .

[0098] The polymer prepared with the composition disclosed herein can have a weight average molecular weight (Mw) of 10,000 g / mol to 1,000,000 g / mol. All individual values ​​and subranges of 10,000 g / mol to 1,000,000 g / mol are included; for example, the polymer can have a Mw with a lower limit of 10,000 g / mol, 50,000 g / mol, or 100,000 g / mol to an upper limit of 1,000,000 g / mol, 750,000 g / mol, or 500,000 g / mol. As known in the art, Mw can be determined by gel permeation chromatography (GPC). GPC is discussed herein.

[0099] The polymers prepared with the compositions disclosed herein can have a number average molecular weight (Mn) of 5,000 g / mol to 300,000 g / mol. All individual values ​​and subranges of 5,000 g / mol to 300,000 g / mol are included; for example, the polymer can have a Mn with a lower limit of 5,000 g / mol, 20,000 g / mol, or 40,000 g / mol to an upper limit of 300,000 g / mol, 250,000 g / mol, or 200,000 g / mol. Mn can be determined by GPC.

[0100] The polymers prepared with the compositions disclosed herein may have a Z-average molecular weight (Mz) of 40,000 g / mol to 2,000,000 g / mol. All individual values ​​and subranges of 40,000 g / mol to 2,000,000 g / mol are included; for example, the polymer may have a Mz with a lower limit of 40,000 g / mol, 100,000 g / mol, or 250,000 g / mol to an upper limit of 2,000,000 g / mol, 1,800,000 g / mol, or 1,650,000 g / mol. Mz may be determined by GPC.

[0101] The polymers prepared with the compositions disclosed herein can 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 from 2.00 to 6.00 are included; for example, the polymer can have a Mw / Mn with a lower limit of 2.00, 2.50, or 3.00 to an upper limit of 6.00, 5.50, or 4.50.

[0102] Various aspects of the disclosure are provided as follows.

[0103] Aspect 1 provides an asymmetric metallocene represented by structure (I):

[0104]

[0105] Where: M is Hf or Zr; R 1 Yes (C 1 -C 3 ) alkyl, except 2-methylpropyl (C 4 ) alkyl, or (C 5 ) alkyl; and each X is independently a leaving group; wherein (C 4 ) The alkyl group is selected from butyl, 1-methylpropyl and 1,1-dimethylethyl.

[0106] Aspect 2 provides the asymmetric metallocene according to aspect 1, wherein M is Hf, and the asymmetric metallocene is represented by structure (Ia):

[0107]

[0108] Where: R 1 As defined in claim 1, and wherein each X is independently selected from halogen, (C 1 -C 5 ) alkyl, CH 2 SiMe 3 and a benzyl leaving group.

[0109] Aspect 3 provides the asymmetric metallocene according to aspect 1, wherein M is Zr, and the asymmetric metallocene is represented by structure (Ib):

[0110]

[0111] Where: R 1 As defined in claim 1, and wherein each X is independently selected from halogen, (C 1 -C 5 ) alkyl, CH 2 SiMe 3 and a benzyl leaving group.

[0112] Aspect 4 provides the asymmetric metallocene according to any one of aspects 1 to 3, wherein R 1 For (C 1 -C 3 ) alkyl, wherein (C 1 -C 3 ) alkyl is (C 3 ) alkyl, ethyl or methyl; and wherein (C 3 ) alkyl is selected from 1-methylethyl and n-propyl; or wherein R 1 is not 2-methylpropyl (C 4 ) alkyl; or wherein R 1 For (C 5 )alkyl.

[0113] Aspect 5 provides the asymmetric metallocene according to any one of aspects 1 to 4, wherein each X is Cl or each X is CH 3 .

[0114] Aspect 6 provides the asymmetric metallocene according to aspect 1, wherein the asymmetric metallocene is selected from the group consisting of:

[0115] Hafnium asymmetric metallocenes represented by structures (II) to (IV):

[0116]

[0117]

[0118] or zirconium asymmetric metallocenes represented by structures (V) to (VII):

[0119]

[0120] Wherein in structures (II) to (VII), each X is Cl or each X is CH 3 .

[0121] Aspect 7 provides a method for synthesizing the asymmetric metallocene according to any one of aspects 1 to 6, the method comprising:

[0122] The hafnium complex or the zirconium complex is contacted with an alkali metal complex, wherein the alkali metal complex is represented by the following structure:

[0123]

[0124] wherein M' is lithium, sodium or potassium, and

[0125] The hafnium complex or zirconium complex is represented by one of the following structures:

[0126]

[0127] Where M is Hf or Zr, and R 1 As defined in the above claims (e.g., R 1 is propyl); or

[0128] The hafnium complex or the zirconium complex is contacted with an alkali metal complex, wherein the alkali metal complex is represented by the following structure:

[0129]

[0130] Where M' is lithium, sodium or potassium, and R 1 As defined in the above claims; and

[0131] The hafnium complex or zirconium complex is represented by one of the following structures:

[0132]

[0133] Where M is Hf or Zr respectively;

[0134] To prepare the asymmetric metallocene.

[0135] Aspect 8 provides a method according to aspect 7, comprising: reacting an asymmetric metallocene with two molar equivalents of an organomagnesium halide of formula RMg(halide) or one molar equivalent of R 2 Mg contact, where R is (C 1 -C 5 ) alkyl, CH 2 SiMe 3 or benzyl; and the halide is Cl or Br, to prepare an asymmetric metallocene of structure (I), wherein each X is (C 1 -C 5 ) alkyl, CH 2 SiMe 3 or benzyl.

[0136] Aspect 9 provides a metallocene catalyst composition comprising: an asymmetric metallocene according to any one of Aspects 1 to 6, or an asymmetric metallocene prepared by the method according to Aspect 7 or Aspect 8; and an activator (e.g., an alkylaluminoxane, such as methylaluminoxane).

[0137] Aspect 10 provides the metallocene catalyst composition according to aspect 9, further comprising a support (eg, silica, such as hydrophobic fumed silica or dehydrated silica).

[0138] Aspect 11 provides the metallocene catalyst composition according to aspect 10, wherein the composition is a spray-dried metallocene catalyst composition.

[0139] Aspect 12 provides a method for preparing a metallocene catalyst composition according to any one of Aspects 9 to 11, the method comprising: contacting an asymmetric metallocene with an activator but not with a support to obtain a metallocene catalyst composition according to Aspect 9 without a support; or contacting an asymmetric metallocene with an activator and a support to obtain a metallocene catalyst composition according to Aspect 10 with a support; or contacting an asymmetric metallocene with an activator and a support in an inert solvent to obtain a suspension thereof, and spray drying the suspension to obtain a 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 its slurry) to obtain a spray-dried metallocene catalyst composition according to Aspect 11.

[0140] Aspect 13 provides a method for preparing a polyolefin polymer, the method comprising: polymerizing at least one olefin monomer with the metallocene catalyst composition according to any one of aspects 9 to 11 or the metallocene catalyst composition prepared by the method according to aspect 12 to prepare a polyolefin polymer; wherein preferably, the at least one olefin monomer comprises ethylene and an optional comonomer selected from the group consisting of propylene and (C 4 -C 20 )α-olefins.

[0141] Aspect 14 provides a method according to aspect 13, wherein the at least one olefin monomer comprises ethylene and a comonomer; and wherein the polyolefin polymer has a molecular weight comonomer distribution index (MWCDI) from 0.10 to 10.00 as measured by the MWCDI test method described herein; wherein preferably, the comonomer is selected from the group consisting of: 1-butene, 1-hexene and 1-octene.

[0142] Aspect 15 provides a polyolefin polymer prepared by the method according to any one of aspects 13 to 14.

[0143] Example

[0144] 5-(2-methylpropylene)cyclopenta-1,3-diene, which can be represented by the following formula:

[0145]

[0146] was synthesized as follows. In a glove box, pyrrolidine (1.45 g, 10 mol%) was added to a mixture containing isobutylaldehyde (14.6 g, 203 mmol) and cyclopentadiene (13.4 g, 203 mmol) in MeOH-H 2 O (200mL 4 / 1) in a glass container. The contents of the container were transferred to an ice-cold mixture of saline solution and 10mol% AcOH in a narrow graduated cylinder. The organic phase was separated and dried over molecular sieves. The product (5-(2-methylpropylidene)cyclopenta-1,3-diene) was filtered to obtain a bright yellow oil which was then used without further purification (16.0 g, 65%). 1 H NMR (400 MHz, CDCl 3 )δ:6.54(tdd,J=5.4,3.8,2.5Hz,2H),6.51–6.44(m,1H),6.29–6.17(m,2H),3.02(dp,J=10.0,6.6Hz,1H),1.15(d,J=6.6Hz,6H). 13 C NMR (101 MHz, CDCl 3 )δ:149.88,143.69,133.08,130.87,126.06,119.36,30.58,23.24.

[0147] Isobutylcyclopentadienyllithium, which can be represented by the following formula:

[0148]

[0149] are synthesized as follows.

[0150] Et 2 O (250 mL) was added to the container. 5-(2-methylpropylidene)cyclopenta-1,3-diene (16.0 g, 133 mmol) was added to the contents of the container while stirring. LiAlH 4 (33 mL, 4M Et 2 O solution) was added dropwise to the contents of the container while stirring. Foaming was observed. A white solid precipitated during the addition, and as LiAlH4 The addition was continued and the yellow color gradually faded. The addition was stopped once the solution became only light yellow. The product, isobutylcyclopentadienyllithium, was observed to be a white solid and collected by filtration and washed with Et 2 O and dried under vacuum (13.7 g, 80%).

[0151] Hafnium complex I, which can be represented by the following formula:

[0152]

[0153] are synthesized as follows.

[0154] Hafnium tetrachloride (0.33 g, 1.0 mmol) and bis(isobutylcyclopentadienyl)hafnium dichloride (0.50 g, 1.0 mmol) were combined in a large screw cap container. The contents of the container evolved into a viscous brown liquid when heated. Colorless vapor began to appear on the side of the container at about 150°C. The heating was adjusted to 150°C at this time. A white solid began to form at the colorless steam pipe. After about 5 minutes, the container was stopped and cooled under a nitrogen atmosphere. The white solid was manually scraped off the container 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 batch of white solid was obtained and combined with the first group of isolated materials to obtain complex I (0.59 g, 72%). 1 H NMR (400 MHz, C 6 D 6 )δ5.81(t,J=2.7Hz,2H),5.75(t,J=2.7Hz,2H),2.27(d,J=7.0Hz,3H),1.35(dq,J=13.5,6.7Hz,1H),0.59(d,J=6.6Hz,8H).

[0155] 13 C NMR (101 MHz, C 6 D 6 )δ134.94,116.61,116.04,38.83,30.18,21.67. 13 C NMR (101 MHz, C 6 D 6 )δ134.94,116.61,116.04,38.83,30.18,21.67.

[0156] Hafnium complex II: (n-propylcyclopentadienyl)hafnium trichloride dimethoxyethane adduct which can be represented by the following formula:

[0157]

[0158] was synthesized as follows. (n-propylcyclopentadienyl)hafnium trichloride dimethoxyethane adduct was synthesized by adapting the procedure described in WO 2016 / 168448 A1 to Harlan.

[0159] Example 1-1 Asymmetric metallocene, which can be represented by the following formula:

[0160]

[0161] are synthesized as follows.

[0162] (n-propylcyclopentadienyl)hafnium trichloride dimethoxyethane adduct (0.15 g, 0.311 mmol) and isobutylcyclopentadienyl lithium (0.022 g, 0.311 mmol) were added to the vessel. 2 O was added to the vessel, and the contents of the vessel were stirred at about 20° C. for about 12 hours. The contents of the vessel were filtered and then concentrated under vacuum to give Example 1-1 (0.145 g, 98%) observed as a white solid. 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, C 6 D 6 ): δ5.81(q,J=2.7Hz,4H),5.65(dt,J=3.8,2.7Hz,4H),2.67–2.59(m,2H),2.56(d,J=7.0Hz,2H), 1.62(dp,J=13.5,6.7Hz,1H), 1.45(h,J=7.5Hz,2H), 0.83(t,J=7.4Hz,3H), 0.79(d,J=6.7Hz,6H). 13 C NMR (101 MHz, C 6 D 6 ): δ116.49,115.52,110.70,110.62,39.88,32.47,30.71,24.41,22.47,14.03.

[0163] Example 1-2, a spray-dried composition, was prepared as follows. In a nitrogen-purged glove box, hydrophobic fumed silica (CABOSIL TS-610; 0.665 g) and toluene (19 g) were added to a container and mixed, followed by the addition of a 10% solution (5.5 g) by weight of methylaluminoxane (MAO) in toluene. The contents of the container were then stirred for about 15 minutes. Example 1-1 (0.024 g) was then added to the container and the contents of the container were stirred for about 45 minutes. The contents of the container were then spray dried using a Buchi Mini Spray Dryer B-290 (set temperature: 185°C; 100°C outlet temperature; 150 rpm pump speed) to provide Example 1-2.

[0164] Example 2-1 Asymmetric metallocene, which can be represented by the following formula:

[0165]

[0166] are synthesized as follows.

[0167] Hafnium complex I (0.100 g, 246 mmol) and methylcyclopentadienyl lithium (0.021 g, 0.246 mmol) were added to the vessel. 2 O was added to the vessel, and the contents of the vessel were stirred at about 20° C. for about 12 hours. The contents of the vessel were filtered, and then concentrated under vacuum to obtain Example 2-1 (0.098 g, 88%). 1 H NMR (400 MHz, C 6 D 6 )δ5.79(t,J=2.7Hz,2H),5.75–5.70(m,1H),5.62(t,J=2.7Hz,1H),5.60(t,J=2.7Hz,1H),2.54(d,J= 7.0Hz, 2H), 2.25 (d, J = 2.5Hz, 1H), 2.18 (s, 3H), 1.60 (dq, J = 13.5, 6.7Hz, 1H), 0.78 (d, J = 6.7Hz, 6H). 1 3 C NMR (101 MHz, C 6 D 6 )δ116.43,116.23,110.71,110.66,39.86,30.71,22.46.

[0168] The spray-dried composition of Example 2-2 was 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 and mixed, followed by the addition of a 10% solution (5.5 grams) by weight of methylaluminoxane (MAO) in toluene. The contents of the container were then stirred for about 15 minutes. Example 2-1 (0.022 grams) was then added to the container and the contents of the container were stirred for about 45 minutes. The contents of the container were then spray dried using a Buchi Mini Spray Dryer B-290 (set temperature: 185°C; 100°C outlet temperature; 150 rpm pump speed) to provide Example 2-2.

[0169] Comparative Example A-1, a hafnium metallocene with the same ligand, was prepared as follows. Bis-(n-propylcyclopentadienyl)-hafnium dichloride was commercially available from TCI; one skilled in the art can easily convert it to bis(n-propylcyclopentadienyl)hafnium dimethyl by reaction with a methylating agent such as a Grignard reagent, e.g., methylmagnesium bromide.

[0170] Comparative Example A-1 can be represented by the following formula:

[0171]

[0172] Comparative Example A-2 (spray-dried composition) was prepared 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 and mixed, followed by the addition of a 10% solution (22 grams) by weight of methylaluminoxane (MAO) in toluene. The contents of the container were then stirred for about 15 minutes. Comparative Example A-1 (0.110 grams) was then added to the container and the contents of the container were stirred for about 45 minutes. The contents of the container were then spray dried using a Buchi Mini Spray Dryer B-290 (set temperature: 185°C; 100°C outlet temperature; 150 rpm pump speed) to provide Comparative Example A-2.

[0173] Example 3-1 is a prophetic example of an asymmetric metallocene which can be represented by the formula:

[0174]

[0175] One or more embodiments provide for Example 3-1, X is Cl.

[0176] Polymerization is performed as follows. For the corresponding polymerization, dry NaCl (200 g) is loaded into a laboratory-level gas phase polymerization reactor (equipped with a 2-liter stainless steel autoclave of a variable speed mechanical stirrer) and heated to 100 ° C for one hour under a nitrogen stream. The reactor is then purged with nitrogen, the methylaluminoxane supported by silica is added to the reactor as a scavenger, the reactor temperature is adjusted to about the desired temperature, the reactor is sealed, and the contents of the stirring reactor are stirred. The reactor is preloaded to the desired pressure with hydrogen, ethylene and 1-hexene. When reaching a steady state, the catalyst is loaded into the reactor (at the temperature indicated below) to start polymerization. The reactor temperature is maintained at the desired temperature for 60 minutes of polymerization, wherein hydrogen, C 6 / C 2 The ratio and ethylene pressure were kept constant. At the end of the 60-minute polymerization, the reactor was cooled, vented and opened. The resulting mixture was washed with water and methanol and dried. The polymerization conditions are reported in Tables 1-6.

[0177] A number of properties of the polymers prepared using Examples 1-2, 2-2, 4-2, 5-2, 6-2, and Comparative Example A-2 were determined and the results are reported in Tables 1-6. Polymerization productivity (gram polymer / gram catalyst-hour) was determined as the ratio of the polymer produced to the amount of catalyst added to the reactor. Melt index (I 2 ) is determined according to ASTM D1238 (190°C, 2.16kg), the melt index (I 5 ) is determined according to ASTM D1238 (190°C, 5kg), melt index (I 21 ) was determined according to ASTM D1238 (190°C, 21.6 kg); the melt 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 a second heating cycle to determine T m . M w 、M n 、M z 、M w / M n (PDI) and M z / M w The comonomer content (e.g., 1-hexene) incorporated into the polymer is determined by fast FT-IR spectroscopy of the dissolved polymer in a GPC measurement, as discussed above in the detailed description. The molecular weight comonomer distribution index (MWCDI) is determined as discussed herein.

[0178] Table 1

[0179]

[0180] The data in Table 1 illustrate that the polymers prepared with each of Examples 1-2 and 2-2 have an improved (ie, greater) molecular weight comonomer distribution index (MWCDI) compared to the polymer prepared with Comparative Example A-2.

[0181] Figure 1A Data graphs for determining the MWCDI for Example 1-2 (MWCDI = 5.85) and for determining the MWCDI for Comparative Example A-2 (MWCDI = 3.60) are shown, as shown in Table 1. Data graph 102 corresponds to the determination of the MWCDI for Example 1-2. Data graph 104 corresponds to the determination of the MWCDI for Comparative Example A-2.

[0182] Table 2

[0183]

[0184] The data in Table 2 illustrate that the polymers prepared with each of Examples 1-2 and 2-2 have an improved (ie, greater) molecular weight comonomer distribution index (MWCDI) compared to the polymer prepared with Comparative Example A-2.

[0185] Figure 1B Data graphs for determining the MWCDI for Example 1-2 (MWCDI = 2.13) and for determining the MWCDI for Comparative Example A-2 (MWCDI = 1.67) are shown as shown in Table 2. Data graph 106 corresponds to the determination of the MWCDI for Example 1-2. Data graph 106 corresponds to the determination of the MWCDI for Comparative Example A-2.

[0186] Example 4-1 Asymmetric metallocene, which can be represented by the following formula:

[0187]

[0188] Synthesized as follows. A solution of isobutylcyclopentadienyl lithium (0.10 g, 0.72 mmol) in THF (5 mL) is slowly added to a vial containing a solution of (methylcyclopentadienyl) zirconium trichloride (0.2 g, 0.72 mmol) in THF (5 mL), and stirred at room temperature for about 12 hours. Then, the solvent is removed by vacuum, and the residue is redissolved in toluene (10 mL), and filtered through a syringe filter. The solution is then vacuum concentrated to about ~ 2 mL, and pentane (10 mL) is added, resulting in the formation of a white precipitate. The collected solid is washed with pentane (2 × 5 mL), and dried under vacuum to obtain Example 4-1 (0.22 g, 84%).

[0189] 1 H NMR (400 MHz, benzene-d 6 )δ5.88(t,J=2.56Hz,2H),5.81(t,J=2.68Hz,2H),5.70(t,J=2.83Hz,2H),5.67(t,J=2 .83Hz, 2H), 2.52 (d, J = 7.10Hz, 2H), 2.13 (s, 3H), 1.61 (tq, 1H), 0.78 (d, J = 6.72Hz, 6H).

[0190] Example 4-2, a spray-dried composition, was prepared as follows. In a nitrogen-purged glove box, Cabosil TS-610 hydrophobic fumed silica (1.38 g) was slurried in toluene (36 g) until fully dispersed. A 10 wt % solution of MAO in toluene (11 g) was then added and stirred for 15 minutes. Example 4-1 (0.030 g) was then added and stirred for 30 to 60 minutes. A Büchi Mini Spray Dryer B-290 with the following operating parameters was used to spray dry the mixture to provide Example 4-2: set temperature 185°C, outlet temperature 100°C, aspirator 95, and pump speed 150 revolutions per minute (rpm).

[0191] Example 5-1 Asymmetric metallocene, which can be represented by the following formula:

[0192]

[0193] Synthesized as follows. A solution of isobutylcyclopentadienyl lithium (0.09 g, 0.57 mmol) in THF (5 mL) is slowly added to a vial containing a solution of (ethylcyclopentadienyl) zirconium trichloride (0.2 g, 0.59 mmol) in THF (5 mL), and stirred at room temperature for about 12 hours. Then, the solvent is removed by vacuum, and the residue is redissolved in toluene (10 mL), and filtered through a syringe filter. The solution is then vacuum concentrated to about ~ 2 mL, and pentane (10 mL) is added, resulting in the formation of a white precipitate. The collected solid is washed with pentane (2 × 5 mL), and dried under vacuum to obtain Example 5-1 (0.13 g, 58%).

[0194] 1 H NMR (400 MHz, benzene-d 6)δ5.87(m,4H),5.70(m,4H),2.61(q,2H),2.52(d,J=7.10Hz,2H),1.61(tq,1H),1.04(t,J=7.36Hz,3H),0.78(d,J=6.66Hz,6H).

[0195] Example 5-2, a spray-dried composition, was prepared as follows. In a nitrogen-purged glove box, Cabosil TS-610 hydrophobic fumed silica (1.32 g) was slurried in toluene (34 g) until fully dispersed. A 10 wt % solution of MAO in toluene (10.5 g) was then added and stirred for 15 minutes. Example 5-1 (0.030 g) was then added and stirred for 30 to 60 minutes. A Büchi Mini Spray Dryer B-290 with the following operating parameters was used to spray dry the mixture to provide Example 5-2: set temperature 185°C, outlet temperature 100°C, aspirator 95, and pump speed 150 revolutions per minute (rpm).

[0196] Example 6-1 Asymmetric metallocene, which can be represented by the following formula:

[0197]

[0198] Synthesized as follows. A solution of isobutyl cyclopentadienyl lithium (0.08 g, 0.57 mmol) in THF (5 mL) is slowly added to a vial containing a solution of (n-propyl cyclopentadienyl) hafnium trichloride dimethoxyethane adduct (0.2 g, 0.57 mmol) in THF (5 mL), and stirred at room temperature for about 12 hours. Then, the solvent is removed by vacuum, and the residue is redissolved in toluene (10 mL) and filtered through a syringe filter. The solution is then vacuum concentrated to about ~ 2 mL, and pentane (10 mL) is added, resulting in the formation of a white precipitate. The solid is collected, washed with pentane (2 × 5 mL), and dried under vacuum to obtain Example 6-1 (0.20 g, 90%).

[0199] 1 H NMR (400 MHz, benzene-d 6 )δ5.89(m,4H),5.72(m,4H),2.60(t,J=7.74Hz,2H),2.54(d,J=6.97Hz,2H),1. 62 (septet, 1H), 1.45 (tq, 2H), 0.81 (t, J = 7.42Hz, 3H), 0.79 (d, J = 6.58Hz, 6H).

[0200] Example 6-2, a spray-dried composition, was prepared as follows. In a nitrogen-purged glove box, Cabosil TS-610 hydrophobic fumed silica (1.28 g) was slurried in toluene (33 g) until fully dispersed. A 10 wt % solution of MAO in toluene (10.2 g) was then added and stirred for 15 minutes. Example 6-1 (0.030 g) was then added and stirred for 30 to 60 minutes. A Büchi Mini Spray Dryer B-290 with the following operating parameters was used to spray dry the mixture to provide Example 6-2: set temperature 185°C, outlet temperature 100°C, aspirator 95, and pump speed 150 revolutions per minute (rpm).

[0201] Table 3

[0202]

[0203] The data in Table 3 illustrate that the polymers prepared using each of Example 4-2, Example 5-2, and Example 6-2 have a reverse comonomer distribution (MWCDI>0).

[0204] Table 4

[0205]

[0206] The data in Table 4 illustrate that the polymers prepared using each of Example 4-2, Example 5-2, and Example 6-2 have a reverse comonomer distribution (MWCDI>0).

[0207] Table 5

[0208]

[0209]

[0210] The data in Table 5 illustrate that the polymers prepared using each of Example 4-2, Example 5-2, and Example 6-2 have a reverse comonomer distribution (MWCDI>0).

[0211] Table 6

[0212]

[0213]

[0214] The data in Table 6 illustrate that the polymers prepared using each of Example 4-2, Example 5-2, and Example 6-2 have a reverse comonomer distribution (MWCDI>0).

Claims

1. An asymmetric metallocene represented by structure (I): in: M is Hf or Zr; R 1 is (C1-C3)alkyl, (C4)alkyl other than 2-methylpropyl, or (C5)alkyl; and each X is independently a leaving group; wherein the (C4)alkyl other than 2-methylpropyl is selected from butyl, 1-methylpropyl and 1,1-dimethylethyl.

2. The asymmetric metallocene according to claim 1, wherein M is Hf, and the asymmetric metallocene is represented by structure (Ia): in: R 1 As defined in claim 1, and wherein each X is independently a leaving group selected from halogen, (C1-C5)alkyl, CH2SiMe3 and benzyl.

3. The asymmetric metallocene according to claim 1, wherein M is Zr, and the asymmetric metallocene is represented by structure (Ib): in: R 1 As defined in claim 1, and wherein each X is independently a leaving group selected from halogen, (C1-C5)alkyl, CH2SiMe3 and benzyl.

4. The asymmetric metallocene according to any one of claims 1 to 3, wherein R 1 is (C1-C3)alkyl, wherein the (C1-C3)alkyl is (C3)alkyl, ethyl or methyl; and wherein the (C3)alkyl is selected from 1-methylethyl and n-propyl; or wherein R 1 is (C4)alkyl other than 2-methylpropyl; or wherein R 1 It is a (C5) alkyl group.

5. The asymmetric metallocene according to any one of claims 1 to 4, wherein each X is Cl or each X is CH3.

6. The asymmetric metallocene according to claim 1, wherein the asymmetric metallocene is selected from the group consisting of: Hafnium asymmetric metallocenes represented by structures (II) to (IV): or zirconium asymmetric metallocenes represented by structures (V) to (VII): Wherein in structures (II) to (VII), each X is Cl or each X is CH3.

7. A method for synthesizing an asymmetric metallocene according to any one of claims 1 to 6, wherein each X is Cl, the method comprising: The hafnium complex or the zirconium complex is contacted with an alkali metal complex, wherein the alkali metal complex is represented by the following structure: wherein M' is lithium, sodium or potassium, and The hafnium complex or zirconium complex is represented by one of the following structures: Where M is Hf or Zr, and R 1 as defined in the above claims; or The hafnium complex or the zirconium complex is contacted with an alkali metal complex, wherein the alkali metal complex is represented by the following structure: Where M' is lithium, sodium or potassium, and R 1 As defined in the above claims; and The hafnium complex or the zirconium complex is represented by one of the following structures: Where M is Hf or Zr respectively; To prepare the asymmetric metallocene.

8. The method according to claim 7, comprising: The asymmetric metallocene is contacted with two molar equivalents of an organomagnesium halide of formula RMg(halide) or one molar equivalent of R2Mg, wherein R is (C1-C5)alkyl, CH2SiMe3 or benzyl; and the halide is Cl or Br, to prepare an asymmetric metallocene of structure (I), wherein each X is (C1-C5)alkyl, CH2SiMe3 or benzyl.

9. A metallocene catalyst composition, comprising: The asymmetric metallocene according to any one of claims 1 to 6, or the asymmetric metallocene prepared by the method according to claim 7 or claim 8; and Activator. 10 . The metallocene catalyst composition according to claim 9 , further comprising a carrier.

11. The metallocene catalyst composition of claim 10, wherein the composition is a spray-dried metallocene catalyst composition.

12. A method for preparing a metallocene catalyst composition according to any one of claims 9 to 11, the method comprising: contacting the asymmetric metallocene with the activator but without the support to obtain the metallocene catalyst composition according to claim 9 without a support; or contacting the asymmetric metallocene with the activator and the carrier to obtain the metallocene catalyst composition according to claim 10 with the carrier; Alternatively, the asymmetric metallocene is contacted with the activator and the support in an inert solvent to obtain a suspension thereof, and the suspension is spray-dried to obtain the spray-dried metallocene catalyst composition according to claim 11; or the asymmetric metallocene in an inert solvent is contacted with a supported or spray-dried activator (or its slurry) to obtain the spray-dried metallocene catalyst composition according to claim 11.

13. A method for preparing a polyolefin polymer, the method comprising: At least one olefin monomer is polymerized with the metallocene catalyst composition according to any one of claims 9 to 11 or the metallocene catalyst composition prepared by the method according to claim 12 to prepare the polyolefin polymer; wherein preferably, the at least one olefin monomer comprises ethylene and optionally a comonomer selected from the group consisting of propylene and (C4-C 20 )α-olefins.

14. The method of claim 13, wherein the at least one olefin monomer comprises ethylene and the comonomer; and wherein 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; wherein preferably, the comonomer is selected from the group consisting of: 1-butene, 1-hexene and 1-octene.

15. A polyolefin polymer prepared by the method according to any one of claims 13 to 14.

Images