Catalyst system and method for manufacturing polyethylene using the same

Abstract

Embodiments of the present application relate to a precatalyst comprising a metal-ligand complex having the structure of the following formula (I), and a catalytic system comprising the precatalyst:

Description

Technology Field

[0001] Cross-reference of related applications

[0002] The present application claims priority to U.S. Provisional Application No. 63 / 031,638 filed May 29, 2020, U.S. Provisional Application No. 63 / 143,324 filed January 29, 2021, and U.S. Provisional Application No. 63 / 143,333 filed January 29, 2021, each of which is incorporated by reference in its entirety.

[0003] Technology field

[0004] The embodiments of the present disclosure generally relate to a method for producing polyethylene, and in particular to ethylene and optionally one or more (C3-C) in a gas-phase polymerization reactor. 12 This relates to a method of contacting an α-olefin comonomer with a silyl-crosslinked bis-phenylphenoxy catalyst system. Background Technology

[0005] Since the discovery by Ziegler and Natta regarding heterogeneous olefin polymerization, global polyolefin production reached approximately 150 million tons per year in 2015 and continues to increase due to market demand. In polyolefin polymerization methods, catalytic systems can contribute to the characteristics and properties of the polyolefins. For example, catalytic systems containing bis-phenylphenoxy (BPP) metal-ligand complexes can produce polyolefins having a flat or reverse short-chain branching distribution (SCBD), a relatively high level of comonomer incorporation, a high intrinsic molecular weight, and / or a narrow-to-medium molecular weight distribution (MWD).

[0006] However, when used in some polymerization methods, such as gas-phase polymerization, catalyst systems containing BPP metal-ligand complexes can generally exhibit poor productivity. That is, catalyst systems containing BPP metal-ligand complexes can generally produce less polymer compared to the amount of catalyst used. Therefore, the use of catalyst systems containing BPP metal-ligand complexes may not be commercially feasible in gas-phase polymerization methods.

[0007] Therefore, there is a continuous demand for catalyst systems that are suitable for use in gas-phase reactors and have improved productivity when used in gas-phase polymerization methods. The embodiments of the present disclosure address this demand by providing a catalyst system that can be used in gas-phase polymerization methods and exhibits significantly increased productivity compared to similar catalyst systems comprising BPP metal-ligand complexes without silicon-containing crosslinking.

[0008] In addition, ethylene copolymer resins (also referred to as poly(ethylene-co-1-alkene)) generally have a short-chain branched distribution (SCBD) or a comonomer distribution. Many ethylene copolymers have a reverse SCBD or reverse comonomer distribution, where the weight percentage of comonomers decreases as the molecular weight of the ethylene copolymer increases. However, producing copolymers with an increase in weight percentage (weight%) of comonomers as the molecular weight (MW) of the polymer chain increases improves performance in many applications.

[0009] Reverse comonomer distribution is generally achieved using a dual reactor configuration and a single or dual catalyst process. In a dual reactor process, a single catalyst can be used to produce high molecular weight, low-density components (containing a higher wt% comonomer) and low molecular weight, high-density components (containing a lower wt% comonomer) in separate reactors through independent process control in the two reactors. The result is a bimodal resin having a net reverse SCBD across the bimodal distribution. In the case of a dual catalyst single reactor process, one catalyst produces the high molecular weight, low-density components, while the other catalyst produces the low molecular weight, high-density components, resulting in a bimodal product with reverse SCBD.

[0010] Embodiments of this disclosure include a method for producing an ethylene-based copolymer having an inverse comonomer distribution. In the embodiment, the method comprises a reactor temperature of 150°C or lower and one or more (C3-C) for ethylene. 12 ethylene and one or more (C3-C) α-olefin comonomers in the presence of a catalyst system in a single gas-phase polymerization reactor at a molar feed ratio of 0.020 or less. 12 )complicates polymerizing α-olefin comonomers: wherein the catalyst system comprises an active metal-ligand complex having a structure according to chemical formula (Ia); and the ethylene copolymer has a unimodal molecular weight distribution measured by gel permeation chromatography (GPC, e.g., conventional GPC) and a molecular weight comonomer distribution index greater than 0 measured by rapid FT-IR spectroscopy of the dissolved polymer of the GPC measurement.

[0011] In one or more embodiments, the catalytic system comprises an activated metal-ligand complex disposed on one or more supporting materials. The activated metal-ligand complex has a structure according to the following chemical formula (Ia):

[0012]

[0013] In chemical formula (I), A - is an anion. M is titanium, zirconium, or hafnium; (X) n The subscript n of is 1, 2, or 3; each X is independently unsaturated (C2-C 50 )hydrocarbon, unsaturated (C2-C 50 )heterohydrocarbon, (C1-C 50 )hydrocarville, (C1-C 50 )heterohydrocarbyl, ( C6-C 50 )aryl, ( C4-C 50 )heteroaryl, halogen, -N(R N )2, and -N(R N )COR C It is a monoligand selected from; and the metal-ligand complex of formula (I) is overall charge-neutral.

[0014] In chemical formula (I), each Z is independently -O-, -S-, (C6-C 50 )aryl, ( C4-C 50 )heteroaryl, N(C1-C 40 )hydrocarbyl, and P(C1-C 40 ) is selected from hydrocarvil.

[0015] In chemical formula (I), R 1 and R 16 is independently (C6-C 50 )aryl, ( C4-C 50 )heteroaryl, (C1-C 40 )alkyl, (C3-C 40 ) selected from heteroalkyl, radical having the following formula (II), radical having the following formula (III), and radical having the following formula (IV):

[0016]

[0017] In chemical formulas (II), (III), and (IV), R 31-35 , R 41-48 , and R51-59 is independently -H, (C1-C 50 )hydrocarville, (C1-C 50 )heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or is selected from halogen.

[0018] In chemical formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 is independently -H, (C1-C 50 )hydrocarville, (C1-C 50 )heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R CC(O)N(R)-, (R C )2NC(O)-, and is selected from halogens.

[0019] In chemical formula (I), R 17 and R 18 is independently -(CR C 2) m Selected from -, where subscript m is 1 to 10, and -(CR C 2) m of R C is -H, (C1-C 10 It is an alkyl.

[0020] In chemical formula (I), R 19 and R 20 is independently linear or branched (C1-C 20 Selected from alkyls.

[0021] In chemical formulas (I), (II), (III), and (IV), respectively, R C , R P , and R N is independently -H, (C1-C 50 )hydrocarbyl, and (C1-C 50 ) is selected from heterohydrocarbyl.

[0022] An embodiment of the present disclosure includes a method for preparing a catalytic system. The method comprises contacting one or more support materials, one or more activators, and a metal-ligand complex in an inert hydrocarbon solvent to produce a catalytic system.

[0023] Embodiments of the present disclosure include a method for manufacturing polyethylene. The method involves ethylene and optionally one or more (C3-C) in a gas-phase polymerization reactor. 12 )It includes contacting an α-olefin comonomer with a catalyst system. The catalyst system comprises a metal-ligand complex disposed on one or more support materials. Brief explanation of the drawing

[0024] Figure 1 is a graph depicting the inverse comonomer distribution and molecular weight distribution of Example 1 and Example 4 of the present invention. Figure 2 is a graph depicting the inverse comonomer distribution and molecular weight distribution of Example 12 of the present invention. Figure 3 is a graph depicting the inverse comonomer distribution and molecular weight distribution of Example 13 of the present invention. Figure 4 is a graph depicting the inverse comonomer distribution and molecular weight distribution of Example 15 and Example 16 of the present invention. Specific details for implementing the invention

[0025] Specific embodiments of a procatalyst, a catalytic system, a method for manufacturing a catalytic system, and a method for manufacturing polyethylene will now be described. However, it should be understood that the systems, methods, and processes of this disclosure may be embodied in different forms and should not be construed as being limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided to ensure that this disclosure is thorough and complete and sufficiently conveys the scope of the subject matter to those skilled in the art.

[0026] Common abbreviations used in this disclosure are listed below:

[0027] Me : Methyl; Et : Ethyl; Ph : Phenyl; Bn : Benzyl; i -Pr : Iso -profile; t -Bu : tert -butyl; t -Oct : tert -Octyl(2,4,4-trimethylpentane-2-yl); Tf : Trifluoromethanesulfonate; THF : Tetrahydrofuran; Et 2 O : Diethyl ether; CH 2 Cl 2: Dichloromethane; CV : Column volume (used in column chromatography); EtOAc : Ethyl acetate; C 6 D 6 : Deuteriumized benzene or benzene- d 6; CDCl 3 : Deuteriumized chloroform; Na 2 SO 4 : Sodium sulfate; MgSO 4 : Magnesium sulfate; HCl : Hydrogen chloride; n -BuLi : Butyl lithium; t -BuLi : tert - Butyl lithium; MAO : Methylaluminoxan; MMAO : Modified methylaluminoxane; GC : Gas chromatography; LC : Liquid chromatography; NMR : Nuclear magnetic resonance; MS : Mass Spectroscopy; mmol : millimoles; mL : milliliters; M : Mol; min or mins : minute; h or hrs : hour; d : Day.

[0028] The term "halogen atom" or "halogen" refers to the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). The term "halide" refers to the anionic form of a halogen atom: fluoride (F - ), chloride (Cl - ), bromide (Br - ) or iodide(I - It means ).

[0029] The term "independently selected" refers to R, for example, R 1 , R 2 , and R3 This may be the same or different (e.g., R 1 , R 2 , and R 3 All can be substituted alkyls; or R 1 and R 2 can be a substituted alkyl, and R 3 It means that it may be an aryl. The chemical name associated with the R group is intended to convey the chemical structure recognized in the art as corresponding to that of the chemical name. As a result, the chemical name is intended not to exclude the structural definition known to those skilled in the art, but to supplement and exemplify it.

[0030] The term "pre-catalyst" means a compound that exhibits catalytic activity when combined with an activator. The term "activator" means a compound that chemically reacts with the pre-catalyst in a manner that converts the pre-catalyst into a catalytically active compound. As used herein, the terms "co-catalyst" and "activator" may be interchangeable and have the same meaning unless otherwise explicitly indicated.

[0031] The term "substitution" refers to at least one hydrogen atom (-H) bonded to a carbon atom of a corresponding unsubstituted compound or functional group being a substituent (e.g., R S It means that it has been replaced by ). The term "-H" means hydrogen or a hydrogen radical that is covalently bonded to another atom. As used in this disclosure, the terms "hydrogen" and "-H" may be interchangeable and have the same meaning unless otherwise explicitly indicated.

[0032] When used to describe specific carbon atom-containing chemical groups, the form "(C x -C y An interpolation expression containing ” means that the unsubstituted form of the chemical group has x to y carbon atoms (including x and y). For example, (C1-C 50)alkyl is an unsubstituted form of an alkyl group having 1 to 50 carbon atoms. In some embodiments and general structures, a specific chemical group is R S It can be substituted with one or more substituents such as. "(C x -C y R defined using the )" insertion phrase S The substituted chemical group is any group R S Depending on its identity, it can contain more than y carbon atoms. For example, "exactly one group R S Replaced with (C1-C 50 )alkyl(in the formula, R S "is phenyl(-C6H5)" can contain 7 to 56 carbon atoms. As a result, "(C x -C y A chemical group defined using the )" insertion is one or more carbon atom-containing substituents R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is all carbon atom-containing substituents R S It is determined by adding the combined sum of the number of carbon atoms from to both x and y.

[0033] term "(C1-C 50 ")hydrocarbyl" refers to a hydrocarbon radical with 1 to 50 carbon atoms, and the term "(C1-C 50 ")hydrocarbylene" means a hydrocarbon 2 radical having 1 to 50 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon 2 radical are aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (having 3 or more carbons, including mono- and poly-cyclic, fused and non-fused polycyclic, and bicyclic), or non-cyclic, and one or more R S It is substituted or unsubstituted as. As used in this disclosure, (C1-C 50 )hydrocarbyl is unsubstituted or substituted (C1-C 50 )alkyl, (C3-C50 )cycloalkyl, (C3-C 25 )cycloalkyl-(C1-C 25 )alkylene, (C6-C 50 )aryl, or (C6-C 25 )aryl-(C1-C 25 It can be an alkylene (e.g., benzyl (-CH2-C6H5)).

[0034] term "(C1-C 50 ")alkyl" refers to a saturated linear or branched hydrocarbon radical containing 1 to 50 carbon atoms. Each (C1-C 50 )alkyl groups are unsubstituted or have one or more R S It can be substituted by. In an embodiment, each hydrogen atom of the hydrocarbon radical is R, for example, trifluoromethyl. S It can be substituted with. Unsubstituted (C1-C 50 Examples of )alkyl groups include unsubstituted (C1-C 20 )alkyl; unsubstituted (C1-C 10 )alkyl; unsubstituted (C1-C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Substituted (C1-C 50 Examples of )alkyl groups include substituted (C1-C 20 )alkyl, substituted (C1-C 10 )alkyl, trifluoromethyl, and [C 45 ]alkyl. The term "[C 45 ]alkyl means that, including substituents, up to 45 carbon atoms are present in the radical, and one R, e.g., (C1-C5)alkyl, e.g., methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl. S Replaced with (C 27 -C 40 It is an alkyl.

[0035] term "(C3-C 50 )cycloalkyl" is unsubstituted or has one or more RS It refers to a saturated cyclic hydrocarbon radical having 3 to 50 carbon atoms substituted with . other cycloalkyl groups (e.g., (C x -C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S It is defined in a manner similar to that which is substituted. Unsubstituted (C3-C 50 Examples of )cycloalkyls are unsubstituted (C3-C 20 )cycloalkyl, unsubstituted (C3-C 10 ) are cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substituted (C3-C 50 Examples of )cycloalkyls are substituted (C3-C 20 )cycloalkyl, substituted (C3-C 10 )cycloalkyl, and 1-fluorocyclohexyl.

[0036] term "(C6-C 50 )aryl" is unsubstituted or (one or more R S It refers to a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical having 6 to 50 carbon atoms (wherein at least 6 to 14 of the carbon atoms are aromatic ring carbon atoms) substituted. A monocyclic aromatic hydrocarbon radical contains one aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. Where a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. Other rings or rings of the aromatic radical may independently be fused or unfused and may be aromatic or non-aromatic. Unsubstituted (C6-C 50 Examples of aryls include: unsubstituted (C6-C 20 )aryl, unsubstituted (C6-C 18)aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6-C 50 Examples of aryls include: substituted (C1-C 20 )aryl; substituted (C6-C 18 )aryl; 2,4-bis([C 20 ]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluorene-9-on-l-yl.

[0037] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms are O, S, S(O), and S(O). 2, Si(R C ) 2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -Si(R C )-(among the equations, each R C and each R P is unsubstituted (C1-C 18 )hydrocarbyl or -H, and each R N It is unsubstituted (C1-C 18 Includes )hydrocarbyl). The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by heteroatoms. The term "(C1-C 50 ")heterohydrocarbyl" refers to a heterohydrocarbon radical with 1 to 50 carbon atoms, and the term "(C1-C 50 "Heterohydrocarbylene" refers to a heterohydrocarbon 2-radical consisting of 1 to 50 carbon atoms. (C1-C 50 )heterohydrocarbyl or (C1-C 50The heterohydrocarbon of )heterohydrocarbylene has one or more heteroatoms. The radicals of heterohydrocarbylene may be on carbon atoms or heteroatoms. The two radicals of heterohydrocarbylene may be on a single carbon atom or a single heteroatom. Additionally, of the two radicals, one of the radicals may be on a carbon atom and the other may be on a different carbon atom; one of the two radicals may be on a carbon atom and the other may be on a heteroatom; or one of the two radicals may be on a heteroatom and the other may be on a different heteroatom. Each (C1-C 50 )heterohydrocarbyl and (C1-C 50 )heterohydrocarbylene is unsubstituted or (one or more R S It may be substituted by) aromatic or non-aromatic, saturated or unsaturated, straight or branched, cyclic (including monocyclic and polycyclic, fused and unfused polycyclic) or non-cyclic.

[0038] term "(C4-C 50 )heteroaryl" is unsubstituted or (one or more R S It refers to a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical having 4 to 50 total carbon atoms and 1 to 10 heteroatoms, substituted by ( ). A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical has two rings; and a tricyclic heteroaromatic hydrocarbon radical has three rings. Where a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings of the radical is heteroaromatic. Other rings or rings of the heteroaromatic radical may independently be fused or unfused and may be aromatic or non-aromatic. Other heteroaryl groups (e.g., generally (C x-C y )heteroaryl, e.g. (C4-C 12 A )heteroaryl) has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or has one or more than one R SIt is defined in a manner similar to being substituted. Monocyclic heteroaromatic hydrocarbon radicals are 5-membered or 6-membered rings. A 5-membered ring has 5 - h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3, or 4; each heteroatom can be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals are pyrrole-1-yl; pyrrole-2-yl; furan-3-yl; thiophene-2-yl; pyrazole-1-yl; isoxazole-2-yl; isothiazol-5-yl; imidazole-2-yl; oxazole-4-yl; thiazole-2-yl; 1,2,4-triazole-1-yl; 1,3,4-oxadiazole-2-yl; 1,3,4-thiadiazole-2-yl; Includes tetrazole-1-yl; tetrazole-2-yl; and tetrazole-5-yl. The 6-membered ring has 6 - h carbon atoms, where h is the number of heteroatoms, which can be 1 or 2, and the heteroatoms can be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridine-2-yl; pyrimidine-2-yl; and pyrazine-2-yl. Bicyclic heteroaromatic hydrocarbon radicals may be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indole-1-yl; and benzimidazole-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinoline-2-yl; and isoquinoline-1-yl. The tricyclic heteroaromatic hydrocarbon radical can be a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6-ring system. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indole-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indole-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazole-9-yl. An example of a fused 6,6,6-ring system is acridin-9-yl.

[0039] The term "polymer" refers to a polymeric compound produced by polymerizing identical or different types of monomers. Accordingly, the general term polymer includes homopolymers, which are polymers produced by polymerizing only a single monomer, and copolymers, which are polymers produced by polymerizing two or more different monomers.

[0040] The term "hybrid polymer" refers to a polymer produced by the polymerization of at least two different types of monomers. Thus, the general term hybrid polymer includes copolymers and other polymers produced by polymerizing more than two different monomers, such as terpolymers.

[0041] The terms "polyolefin," "polyolefin polymer," and "polyolefin resin" refer to simple olefins (also represented as alkenes, which have the general chemical formula C n H 2n It refers to a polymer produced by polymerizing monomers having (

[0042] The terms “ethylene copolymer,” “polyethylene,” and “ethylene polymer” refer to polyolefins containing more than 50 molar percentage (%) of units derived from ethylene monomers, including polyethylene homopolymers and copolymers. Common forms of polyethylene known in the art include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), very low-density polyethylene (VLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE).

[0043] The term "molecular weight distribution" refers to the ratio of polymers with two different molecular weights. The general term molecular weight distribution is "molecular weight distribution (M w / M n The number average molecular weight (M) of a polymer, which can also be expressed as ” n Weight average molecular weight (M) of the polymer for ) w The ratio of ), and "molecular weight distribution (M z / M w The weight-average molecular weight (M) of a polymer that can also be expressed as )" w The z-average molecular weight (M) of the polymer for ) z Includes the ratio of ).

[0044] The term "composition" refers to a mixture of substances including not only the composition but also reaction products and decomposition products formed from the material of the composition.

[0045] The terms “comprising,” “having,” and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether specifically disclosed. To avoid doubt, any composition claimed through the use of the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymeric or not, unless otherwise stated. In contrast, the term “essentially consisting of” excludes any other components, steps, or procedures from the category of any subsequent description, except those not essential to feasibility. The term “consisting of” excludes any components, steps, or procedures that are not specifically described or enumerated.

[0046] In an embodiment, the catalyst system comprises a total catalyst. The total catalyst comprises a metal-ligand complex. The metal-ligand complex may have a structure according to the following chemical formula (I):

[0047]

[0048] In one or more embodiments, the catalytic system comprises an active metal-ligand complex having a structure according to the following chemical formula (Ia):

[0049]

[0050] Chemical formula (Ia) is an exemplary description of an active catalyst. When the metal-ligand complex of chemical formula (I) is catalytically active by an activator, the metal of the metal-ligand complex may have a positive one (+1) formal charge. In an embodiment where the precatalyst comprises the metal-ligand complex, the metal-ligand complex has a structure according to chemical formula (I) and is charge-neutral overall. In an embodiment where the catalytic system comprises the metal-ligand complex, the metal-ligand complex may have a structure according to chemical formula (Ia) and has a positive one (+1) formal charge overall.

[0051] In formulas (I) and (Ia), M is titanium (Ti), zirconium (Zr), or hafnium (Hf). In embodiments, M is titanium, zirconium, or hafnium, each independently in a form oxidation state of +2, +3, or +4.

[0052] In chemical formulas (I) and (Ia), (X) n The subscript n of is 1, 2, or 3, and each X is independently unsaturated (C2-C 50 )hydrocarbon, unsaturated (C2-C 50 )heterohydrocarbon, (C1-C 50 )hydrocarville, (C1-C 50 )heterohydrocarbyl, ( C6-C 50 )aryl, ( C4-C 50 )heteroaryl, halogen, -N(R N )2, and -N(R N )COR CIt is a monolocate ligand selected from. In embodiments, each X is independently selected from methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chloro. In some embodiments, (X) n The subscript n of is 2, and each X is identical. In other embodiments, at least two Xs are different. For example, (X) n The subscript n of may be 2, and each X may be a different one among methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chloro. In an embodiment, (X) n The subscript n of is 1 or 2, at least two Xs are independently monoanionic monolocate ligands, and a third X is a neutral monolocate ligand if present. In one or more embodiments, (X) n The subscript n of is 2.

[0053] In chemical formula (I), the metal-ligand complex is charge-neutral overall. In chemical formula (Ia), the metal-ligand complex has a positive formal charge of 1 (+1) overall.

[0054] In chemical formulas (I) and (Ia), each Z is independently -O-, -S-, (C6-C 50 )aryl, ( C4-C 50 )heteroaryl, N(C1-C 50 )hydrocarbyl, and P(C1-C 50 )Selected from hydrocarbil. In an embodiment, each Z is the same. For example, each Z can be -O-.

[0055] In chemical formulas (I) and (Ia), R 1 and R 16 is independently (C6-C 50 )aryl, ( C4-C 50 )heteroaryl, (C1-C 50 )alkyl, (C3-C 40) selected from heteroalkyl, radical having the following formula (II), radical having the following formula (III), and radical having the following formula (IV):

[0056]

[0057] In chemical formula (II), R 31 , R 32 , R 33 , R 34 , R 35 is independently -H, (C1-C 50 )hydrocarville, (C1-C 50 )heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or is selected from halogen.

[0058] In chemical formula (III), R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 is independently -H, (C1-C 50 )hydrocarville, (C1-C 50 )heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C, -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or is selected from halogen.

[0059] In chemical formula (IV), R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , and R 59 is independently -H, (C1-C 50 )hydrocarville, (C1-C 50 )heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or is selected from halogen.

[0060] Group R of metal-ligand complexes of chemical formulas (I) and (Ia) 1 and R 16 They are selected independently of each other. For example, R 1 can be selected from radicals having formula (II), formula (III), or formula (IV), and R 16 Silver (C4-C 50) May be heteroaryl or; R 1 can be selected from radicals having formula (II), formula (III), or formula (IV), and R 16 is R 1 It may be selected from radicals having the same or different chemical formula (II), chemical formula (III), or chemical formula (IV). In an embodiment, R 1 and R 16 Both are radicals having the chemical formula (II), where R 31-35 is R 1 and R 16 It is the same or different in. In some embodiments, R 1 and R 16 Both are radicals having the chemical formula (III), where R 41-48 is R 1 and R 16 It is the same or different in. In another embodiment, R 1 and R 16 Both are radicals having the chemical formula (IV), where R 51-59 is R 1 and R 16 It is the same or different from.

[0061] In an embodiment, R 1 and R 16 At least one of them is a radical having the chemical formula (II), where R 32 and R 34 At least one of them tert -It is butyl. In some embodiments, R 1 or R 16 If at least one of them is a radical having the chemical formula (III), R 43 and R 46 One or both of tert -butyl and R 41-42 , R 44-45 , and R 47-48 is -H. In another embodiment, R 42 and R 47 One or both of tert-butyl, R 41 , R 43-46 , and R 48 is -H. In some embodiments, R 42 and R 47 Both are -H. In some embodiments, R 41-48 is -H.

[0062] In chemical formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 is independently -H, (C1-C 50 )hydrocarville, (C1-C 50 )heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, and is selected from halogens.

[0063] In some embodiments, R 5 , R 6 , R 7 , and R 8 At least one of them is a halogen atom; R 9 , R 10 , R 11 , and R 12At least one of them is a halogen atom. In some embodiments, R 5 , R 6 , R 7 , and R 8 At least two of them are halogen atoms; R 9 , R 10 , R 11 , and R 12 At least two of them are halogen atoms. In various embodiments, R 5 , R 6 , R 7 , and R 8 At least three of them are halogen atoms; R 9 , R 10 , R 11 , and R 12 At least three of them are halogen atoms.

[0064] In an embodiment, R 3 and R 14 is (C1-C 24 )alkyl. In various embodiments, R 3 and R 14 is (C1-C 20 )alkyl. In some embodiments, R 3 and R 14 is (C4-C 24 )alkyl. In one or more embodiments, R 3 and R 14 is (C8-C 12 )alkyl. In some embodiments, R 3 and R 14 is 1-profile, 2-profile (also Iso -Referred to as propyl), 1,1-dimethyl ethyl (also tert -Referred to as butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-l-butyl, hexyl, 4-methyl-l-pentyl, heptyl, n -Octyl, tert -Octyl (also referred to as 2,4,4-trimethylpentane-2-yl), nonyl, and decyl. In an embodiment, R 3 and R 14 is -OR C and, here R Cis (C1-C 20 ) It is a hydrocarbon, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also Iso - It is referred to as propyl) or 1,1-dimethyl ethyl.

[0065] In an embodiment, R 3 and R 14 is methyl. In another embodiment, R 3 and R 14 is (C4-C 24 )alkyl. In some embodiments, R 8 and R 9 is 1-profile, 2-profile (also Iso -Referred to as propyl), 1,1-dimethyl ethyl (also tert -Referred to as butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-l-butyl, hexyl, 4-methyl-l-pentyl, heptyl, n -Octyl, tert -Octyl (also referred to as 2,4,4-trimethylpentane-2-yl), nonyl, and decyl.

[0066] In some embodiments, R 6 and R 11 is a halogen. In another embodiment, R 6 and R 11 (C1-C 24 )alkyl. In some embodiments, R 6 and R 11 is independently methyl, ethyl, 1-propyl, 2-propyl (also Iso -Referred to as propyl), 1,1-dimethyl ethyl (also tert -Referred to as butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n -Octyl, tert -Selected from octyl (also referred to as 2,4,4-trimethylpentane-2-yl), nonyl, and decyl. In some embodiments, R 6 and R 11 silver tert - It is butyl. In an embodiment, R 6 and R 11-OR C and, here R C is (C1-C 20 )hydrocarbyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also Iso -Referred to as propyl) or 1,1-dimethylethyl. In other embodiments, R 6 and R 11 Silver -SiR C It is 3, and here, each R C is independently (C1-C 20 )hydrocarbyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also Iso - It is referred to as propyl) or 1,1-dimethyl ethyl.

[0067] In some embodiments, R 3 and R 14 is methyl, and R 6 and R 11 is a halogen. In another embodiment, R 6 and R 11 silver tert -It is butyl. In another embodiment, R 3 and R 14 Is tert -Octyl or n It is Octyl.

[0068] In chemical formula (I), R 17 and R 18 is independently -(CR C 2) m - selected from, where the subscript m is 1 to 10. In one or more embodiments, each subscript m is 1 or 2.

[0069] In chemical formula (I), R 19 and R 20 is independently linear or branched (C1-C 20 Selected from )alkyl. In some embodiments, R 19 and R 20 is independently linear or branched (C2-C 20It is selected from )alkyl or (C3-C7)alkyl.

[0070] In chemical formulas (I), (II), (III), and (IV), respectively, R C , R P , and R N is independently -H, (C1-C 50 )hydrocarbyl, and (C1-C 50 ) is selected from heterohydrocarbyl.

[0071] In the embodiments, a precatalyst having the structure of a metal-ligand complex of formula (I) may be conferred catalytic activity by contacting it with an activator or by combining it with an activator. A precatalyst conferred catalytic activity by contacting it with an activator or by combining it with an activator may be represented as a “catalytic system.” That is, as used in this disclosure, a catalytic system may comprise a precatalyst and one or more activators. The term “activator” may include any combination of reagents that increase the rate at which a transition metal compound oligomerizes or polymerizes an unsaturated monomer, e.g., an olefin. The activator may also affect molecular weight, branching degree, comonomer content, or other properties of the oligomer or polymer. The transition metal compound may be activated for oligomerization and / or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and / or polymerization.

[0072] Alumonic acid activators may be used as activators for one or more of the catalyst compositions. Alumonic acid(s) or aluminoxan(s) are generally oligomeric compounds containing a --Al(R)--O-- subunit, where R is an alkyl group. Examples of alumonic acids include methylalumonic acid (MAO), modified methylalumonic acid (MMAO), ethylalumonic acid, and isobutylalumonic acid. Alkylalumonic acids and modified alkylalumonic acids are suitable as catalyst activators, particularly when the extractable ligand is a halide. Mixtures of different alumonic acids and modified alumonic acids may also be used. For further detailed explanation, U.S. Patents No. 4,665,208; No. 4,952,540; No. 5,041,584; No. 5,091,352; No. 5,206,199; Refer to Patent No. 5,204,419; No. 4,874,734; No. 4,924,018; No. 4,908,463; No. 4,968,827; No. 5,329,032; No. 5,248,801; No. 5,235,081; No. 5,157,137; No. 5,103,031; and European Patents EP 0 561 476; EP 0 279 586; EP 0 516 476; EP 0 594 218; and International Publication WO 94 / 10180.

[0073] When the activator is alumonic acid (modified or unmodified), the maximum amount of activator can be selected to be a 5000-fold molar excess of Al / M relative to the catalyst precursor (per metal catalyst site). Alternatively, or additionally, the minimum amount of activator-to-catalyst-precursor can be set to a 1:1 molar ratio.

[0074] Aluminum alkyl or organoaluminum compounds that can be used as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, etc.

[0075] In an embodiment, the metal-ligand complex, the activator, or both may be disposed on one or more support materials. For example, the metal-ligand complex may be deposited on one or more support materials, come into contact with them, vaporize together with them, bind to them, be incorporated into them, or be adsorbed or absorbed into or on them. The metal-ligand complex activator, or both, may be combined with one or more support materials using one of the support methods well known in the art or described below. The metal-ligand complex activator, or both, as used in this disclosure, may be in a supported form, for example, when deposited on one or more support materials, come into contact with them, be incorporated into them, or be adsorbed or absorbed into or on them.

[0076] Suitable supporting materials, such as inorganic oxides, comprise oxides of metals of Group 2, 3, 4, 5, 13, or 14 of the IUPAC periodic table. In embodiments, the supporting material comprises silica, fuming silica, alumina (e.g., described in International Patent Application No. 1999 / 060033), silica-alumina, and mixtures thereof, which may or may not be dehydrated. The fuming silica may be hydrophilic (untreated) or alternatively hydrophobic (treated). In embodiments, the supporting material is hydrophobic fuming silica, which may be prepared by treating untreated fuming silica with a treatment agent such as dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane. In some embodiments, the support material comprises magnesia, titania, zirconia, magnesium chloride (e.g., described in U.S. Patent No. 5,965,477), montmorillonite (e.g., described in European Patent No. 0 511 665), phylosilicate, zeolite, talc, clay (e.g., described in U.S. Patent No. 6,034,187), and mixtures thereof. In other embodiments, combinations of these support materials, e.g., silica-chromium, silica-alumina, silica-titania, and combinations thereof may be used. Additional support materials may also comprise the porous acrylic polymer described in European Patent No. 0 767 184. Other support materials may also include the nanocomposite described in International Patent Application No. 1999 / 047598; the aerogel described in International Patent Application No. 1999 / 048605; It may include spherulites as described in U.S. Patent No. 5,972,510; and polymeric beads as described in International Patent Application No. 1999 / 050311.

[0077] In an embodiment, the supporting material is 10 square meters / gram (m²). 2 / g) to 700 m 2 Surface area per g, 0.1 cubic meter / gram (cm²) 3 / g) to 4.0 cm3 It has a pore volume of / g and an average particle size of 5 microns (μm) to 500 μm. In some embodiments, the supporting material is 50 m 2 / g to 500 m 2 Surface area of ​​ / g, 0.5 cm² 3 / g to 3.5 cm 3 It has a pore volume of / g and an average particle size of 10 μm to 200 μm. In another embodiment, the support material is 100 m 2 / g to 400 m 2 Surface area of ​​ / g, 0.8 cm² 3 / g to 3.0 cm 3 It may have a pore volume of / g and an average particle size of 5 μm to 100 μm. The average pore size of the supporting material is typically 10 angstroms (Å) to 1,000 Å, e.g., 50 Å to 500 Å or 75 Å to 350 Å.

[0078] Various suitable methods exist for manufacturing the catalytic system of the present disclosure. In one or more embodiments, the method for manufacturing the catalytic system comprises contacting one or more support materials, one or more activators, and a metal-ligand complex in an inert hydrocarbon solvent to produce the catalytic system. In some embodiments, the method for manufacturing the catalytic system may comprise placing one or more activators on one or more support materials to produce a supported activator, and contacting the supported activator with a solution of the metal-ligand complex in an inert hydrocarbon solvent (often referred to as a "trim catalyst" or "trim feed"). For example, in some embodiments, the method for manufacturing the catalytic system comprises contacting a spray-dried supported activator (i.e., a supported activator produced by spray drying) with a solution of the metal-ligand complex in an inert hydrocarbon solvent. In some embodiments, the supported activator may be contained in a slurry, for example, a mineral oil slurry.

[0079] In some embodiments, a method for preparing a catalyst system may comprise mixing one or more support materials, one or more activators, and a metal-ligand complex to produce a catalyst system precursor. The method may also comprise drying the catalyst system precursor to produce a catalyst system. More specifically, the method may comprise preparing a mixture of a metal-ligand complex, one or more support materials, one or more activators, or a combination thereof, and an inert hydrocarbon solvent. The inert hydrocarbon solvent may then be removed from the mixture to produce a metal-ligand complex, one or more activators, or a combination thereof disposed on one or more support materials. In an embodiment, the removal step may be achieved by conventional evaporation of the inert hydrocarbon solvent from the mixture (i.e., a conventional concentration method), which yields an evaporated / supported catalyst system. In another embodiment, the removal step may be achieved by spray-drying the mixture to produce spray-dried particles. It should be understood that the drying and / or removal step may not result in the complete removal of liquid from the produced catalyst system. That is, the catalyst system may contain a remainder of inert hydrocarbon solvent (i.e., 1% to 3% by weight).

[0080] As indicated above, the catalytic system of the present disclosure may be used in a method for producing a polymer, such as polyethylene, through the polymerization of an olefin, such as ethylene. In an embodiment, one or more olefins may be brought into contact with the catalytic system of the present disclosure in a gas phase polymerization reactor, such as a gas phase fluidized bed polymerization reactor. Exemplary gas phase systems are described in U.S. Patents No. 5,665,818; No. 5,677,375; and No. 6,472,484; and European Patents No. 0 517 868 and No. 0 794 200. For example, in some embodiments, ethylene and optionally, one or more (C3-C 12The α-olefin comonomer may be in contact with the catalyst system of the present disclosure in a gas-phase polymerization reactor. The catalyst system may be supplied to the gas-phase polymerization reactor in a pure form (i.e., as a dry solid), as a solution, or as a slurry. For example, in some embodiments, spray-dried particles of the catalyst system may be supplied directly to the gas-phase polymerization reactor. In other embodiments, a solution or slurry of the catalyst system in a solvent, such as an inert hydrocarbon or mineral oil, may be supplied to the reactor. For example, the pre-catalyst may be supplied to the reactor in an inert hydrocarbon solution and the activator may be supplied to the reactor in a mineral oil slurry.

[0081] In an embodiment, the gas phase polymerization reactor comprises a fluidized bed reactor. The fluidized bed reactor may comprise a "reaction zone" and a "rate reduction zone." The reaction zone may comprise a layer of growing polymer particles, formed polymer particles, and a small amount of catalytic system fluidized by a continuous flow of gaseous monomer and diluent to remove the heat of polymerization through the reaction zone. Optionally, a portion of the recirculated gas may be cooled and compressed to form a liquid that increases the heat removal capacity of the circulating gas stream when reintroduced into the reaction zone. A suitable gas flow rate can be easily measured by a simple experiment. The replenishment of gaseous monomer to the circulating gas stream may be at a rate equal to the rate at which the particulate polymer product and the monomers combined therewith can be recovered from the reactor, and the composition of the gas passing through the reactor may be adjusted to essentially maintain a steady-state gas composition within the reaction zone. The gas leaving the reaction zone may pass through a rate reduction zone where entrained particles are removed. Finer entrained particles and dust may be removed in a cyclone and / or microfilter. The gas can be passed through a heat exchanger where the heat of polymerization can be removed, compressed in a compressor, and then returned to the reaction zone. Additional reactor details and methods of operating the reactor are described, for example, in U.S. Patents No. 3,709,853; No. 4,003,712; No. 4,011,382; No. 4,302,566; No. 4,543,399; No. 4,882,400; No. 5,352,749; and No. 5,541,270; European Patent No. 0 802 202; and Belgian Patent No. 839,380.

[0082] In the embodiment, the reactor temperature of the gas phase polymerization reactor is 150°C or lower. For example, the reactor temperature of a gas-phase polymerization reactor is 30°C to 120°C, 30°C to 110°C, 30°C to 100°C, 30°C to 90°C, 30°C to 50°C, 30°C to 40°C, 40°C to 150°C, 40°C to 120°C, 40°C to 110°C, 40°C to 100°C, 40°C to 90°C, 40°C to 50°C, 50°C to 150°C, 50°C to 120°C, 50°C to 110°C, 50°C to 100°C, 50°C to 90°C, 90°C to 150°C, 90°C to 120°C, 90°C to 110°C, 90°C to 100°C, 100°C to It may be 150°C, 100°C to 120°C, 100°C to 110°C, 110°C to 150°C, 110°C to 120°C, or 120°C to 150°C. Generally, the gas phase polymerization reactor may be operated at the highest feasible temperature, taking into account the sintering temperature of the polymer product within the reactor. Regardless of the method used to manufacture polyethylene, the reactor temperature must be below the melting or "sintering" temperature of the polymer product. Consequently, the upper limit temperature may be the melting temperature of the polymer product.

[0083] In an embodiment, the reactor pressure of the gas phase polymerization reactor is 690 kPa (100 psig) to 3,448 kPa (500 psig). For example, the reactor pressure of a gas-phase polymerization reactor is 690 kPa (100 psig) to 2,759 kPa (400 psig), 690 kPa (100 psig) to 2,414 kPa (350 psig), 690 kPa (100 psig) to 1,724 kPa (250 psig), 690 kPa (100 psig) to 1,379 kPa (200 psig), 1,379 kPa (200 psig) to 3,448 kPa (500 psig), 1,379 kPa (200 psig) to 2,759 kPa (400 psig), 1,379 kPa (200 psig) to 2,414 kPa (350 psig), 1,379 It may be kPa (200 psig) to 1,724 kPa (250 psig), 1,724 kPa (250 psig) to 3,448 kPa (500 psig), 1,724 kPa (250 psig) to 2,759 kPa (400 psig), 1,724 kPa (250 psig) to 2,414 kPa (350 psig), 2,414 kPa (350 psig) to 3,448 kPa (500 psig), 2,414 kPa (350 psig) to 2,759 kPa (400 psig), or 2,759 kPa (400 psig) to 3,448 kPa (500 psig).

[0084] In an embodiment, hydrogen gas may be used during polymerization to control the final properties of polyethylene. The amount of hydrogen in the polymerization may be expressed as a molar ratio to the total polymerizable monomer, e.g., ethylene or a blend of ethylene and 1-hexene. The amount of hydrogen used in the polymerization process may be the amount required to achieve the desired properties of polyethylene, e.g., melt flow rate (MFR). In an embodiment, the molar ratio of hydrogen to the total polymerizable monomer (H2:monomer) is greater than 0.0001. For example, the molar ratio of hydrogen to total polymerizable monomer (H2:monomer) is 0.0001 to 10, 0.0001 to 5, 0.0001 to 3, 0.0001 to 0.10, 0.0001 to 0.001, 0.0001 to 0.0005, 0.0005 to 10, 0.0005 to 5, 0.0005 to 3, 0.0005 to 0.10, 0.0005 to 0.001, 0.001 to 10, 0.001 to 5, 0.001 to 3, 0.001 to 0.10, 0.10 to 10, 0.10 to 5, 0.10 to 3, 3 to 10, 3 to It can be 5, or 5 to 10.

[0085] In one or more embodiments, the method uses at least 2,500 grams of polyethylene per gram of catalyst system per hour (g poly / g cat · time) generates. In some embodiments, the method generates 3,000 g poly / g cat · Time; 4,000 g poly / g cat · Time, or 5,000 g poly / g cat · Generates more than time.

[0086] In an embodiment, the catalyst system of the present disclosure may be used to polymerize a single type of olefin to produce a homopolymer. However, additional α-olefins may be incorporated into the polymerization process in other embodiments. Additional α-olefin comonomers typically have 20 or fewer carbon atoms. For example, the catalyst system of the present disclosure comprises ethylene and one or more (C3-C 12 It can be used to polymerize α-olefin comonomers. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-l-pentene. For example, one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or alternatively, from the group consisting of 1-hexene and 1-octene.

[0087] In one or more embodiments, the method produces an ethylene copolymer in which the ratio of the weight-average molecular weight of the ethylene copolymer to the weight percentage comonomer content of the ethylene copolymer is 10,000, 20,000, or 30,000 or more.

[0088] In some embodiments, the method produces an ethylene copolymer having a molecular weight greater than 500,000 g / mol. In some embodiments, the molecular weight of the ethylene copolymer produced is greater than 600,000 g / mol, greater than 700,000 g / mol, or greater than 750,000 g / mol.

[0089] In various embodiments, the molecular weight comonomer distribution is greater than 0 when the reactor temperature is 85°C to 105°C. In one or more embodiments, the molecular weight comonomer distribution is greater than 0 when the molecular weight is greater than 200,000 g / mol.

[0090] In an embodiment, the ethylene copolymer also contains less than 30 weight percent of comonomer incorporation as measured by rapid FT-IR (Fourier Transformer Infrared) spectroscopy of the dissolved polymer as part of a GPC measurement. In some embodiments, the comonomer incorporation is less than 20 weight percent.

[0091] Most ethylene-based copolymers have a comonomer content (i.e., the weight fraction of constituent units derived from 1-alkenes in the copolymer) that varies with the molecular weight of their constituent macromolecules. Basically, if the higher molecular weight fraction of the macromolecule has a lower weight percent comonomer content, this is a normal comonomer distribution with respect to molecular weight. A normal comonomer distribution can also be expressed as a normal short-chain branching distribution (normal SCBD) or a normal molecular weight comonomer distribution index (normal MWCDI). If MWCDI is less than 0, there is a normal MWCDI or normal SCBD. If MWCDI = 0, there is a flat MWCDI or flat SCBD. The MWCDI value is Log(weight-average molecular weight)(Log(M w It is measured from a plot of SCB per 1,000 carbon atoms for )). See U.S. Patent Application Publication US 2017 / 008444 A1.

[0092] If a higher molecular weight fraction has a higher weight% comonomer content, it will be said to have an inverse comonomer distribution with respect to molecular weight. This phenomenon is also represented as an inverse short-chain branching distribution (inverse SCBD), an inverse molecular weight comonomer distribution index (inverse MWCDI), or a broad-orthogonal composition distribution (BOCD). If the MWCDI is greater than 0, there is an inverse comonomer distribution or an inverse SCBD.

[0093] This distribution of comonomer content across molecular weights is represented by plotting the linear regression of comonomer content to weight percentage (wt%) on the y-axis against Log(M) on the x-axis. Wt% comonomer content is measured by rapid Fourier transform-infrared (FT-IR) spectroscopy for dissolved copolymers in gel permeation chromatography (GPC) measurements using an infrared detector. M is the specific x-axis molecular weight point of the Flory distribution of molecular weights measured by GPC, (10 ^ [Log(M)]). In the plot above, the normal comonomer distribution has a negative slope (i.e., the line fitted to data points going from lower Log(M) values ​​to higher Log(M) values ​​(from left to right on the x-axis) slopes downward).

[0094] In an embodiment, one or more (C3-C 12 )α-olefin comonomers may not be derived from propylene. That is, one or more (C3-C 12 )α-olefin comonomers may be substantially free of propylene. The term "substantially free" means that the substance or mixture contains less than 1.0 weight percent of the compound. For example, one or more (C3-C) that may be substantially free of propylene 12 The α-olefin comonomer may contain less than 1.0 wt% of propylene, e.g., less than 0.8 wt% of propylene, less than 0.6 wt% of propylene, less than 0.4 wt% of propylene, or less than 0.2 wt% of propylene.

[0095] In an embodiment, the polyethylene produced, e.g., a homopolymer and / or copolymer (e.g., a copolymer) of ethylene and optionally one or more comonomers, may comprise at least 50 mole percent (mol%) of monomer units derived from ethylene. For example, the polyethylene may comprise at least 60 mole%, at least 70 mole%, at least 80 mole%, or at least 90 mole% of monomer units derived from ethylene. In an embodiment, the polyethylene comprises 50 mole% to 100 mole% of monomer units derived from ethylene. For example, polyethylene may comprise monomer units derived from ethylene in an amount of 50 mol% to 90 mol%, 50 mol% to 80 mol%, 50 mol% to 70 mol%, 50 mol% to 60 mol%, 60 mol% to 100 mol%, 60 mol% to 90 mol%, 60 mol% to 80 mol%, 60 mol% to 70 mol%, 70 mol% to 100 mol%, 70 mol% to 90 mol%, 70 mol% to 80 mol%, 80 mol% to 100 mol%, or 90 mol% to 100 mol%.

[0096] In an embodiment, the polyethylene produced comprises at least 90 mol% monomer units derived from ethylene. For example, the polyethylene may comprise at least 93 mol%, at least 96 mol%, at least 97 mol%, or at least 99 mol% monomer units derived from ethylene. In an embodiment, the polyethylene comprises 90 mol% to 100 mol% monomer units derived from ethylene. For example, polyethylene is 90 mol% to 99.5 mol%, 90 mol% to 99 mol%, 90 mol% to 97 mol%, 90 mol% to 96 mol%, 90 mol% to 93 mol%, 93 mol% to 100 mol%, 93 mol% to 99.5 mol%, 93 mol% to 99 mol%, 93 mol% to 97 mol%, 93 mol% to 96 mol%, 96 mol% to 100 mol%, 96 mol% to 99.5 mol%, 96 mol% to 99 mol%, 96 mol% to 97 mol%, 97 mol% to 100 mol%, 97 mol% to 99.5 mol%, 97 mol% to 99 mol%, 99 mol% to 100 mol%, 97 mol% to 99.5 mol%, 97 mol% to 99 mol%, 99 mol% to 100 mol%, 99 mol% to 99.5 mol%. It may include mole%, or monomer units derived from ethylene in an amount of 99.5 mole% to 100 mole%.

[0097] In an embodiment, the polyethylene produced comprises less than 50 mol% of additional monomer units derived from α-olefin. For example, the polyethylene may comprise less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol% of additional monomer units derived from α-olefin. In an embodiment, the polyethylene comprises 0 mol% to 50 mol% of additional monomer units derived from α-olefin. For example, polyethylene is 0 mol% to 40 mol%, 0 mol% to 30 mol%, 0 mol% to 20 mol%, 0 mol% to 10 mol%, 0 mol% to 5 mol%, 0 mol% to 1 mol%, 1 mol% to 50 mol%, 1 mol% to 40 mol%, 1 mol% to 30 mol%, 1 mol% to 20 mol%, 1 mol% to 10 mol%, 1 mol% to 5 mol%, 5 mol% to 50 mol%, 5 mol% to 40 mol%, 5 mol% to 30 mol%, 5 mol% to 20 mol%, 5 mol% to 10 mol%, 10 mol% to 50 mol%, 10 mol% to 40 mol%, 10 mol% to 30 mol%, 10 mol% to 20 mol%, 20 mol% to 50 It may include additional monomer units derived from α-olefins in mol%, 20 mol% to 40 mol%, 20 mol% to 30 mol%, 30 mol% to 50 mol%, 30 mol% to 40 mol%, or 40 mol% to 50 mol%.

[0098] In an embodiment, the polyethylene produced also comprises one or more additives. The additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, ultraviolet (UV) stabilizers, and combinations thereof. The polyethylene may contain any amount of the additives. In an embodiment, the polyethylene produced also includes, but is not limited to, organic or inorganic fillers, such as calcium carbonate, talc, or Mg(OH)2.

[0099] The generated polyethylene can be used for various products and end-use applications. The generated polyethylene can also be blended with and / or co-extruded with any other polymer. Non-limiting examples of other polymers include linear low-density polyethylene, elastomers, plastomers, high-pressure low-density polyethylene, high-density polyethylene, polypropylene, etc. The generated polyethylene and blends containing the generated polyethylene can be used to produce blow-molded components or products, among other various end-use applications. The generated polyethylene and blends containing the generated polyethylene may be useful for molding operations such as film, sheet, and fiber extrusion and co-extrusion, as well as for blow molding, injection molding, and rotational molding. Films may include blow or cast films formed by co-extrusion or lamination, which are useful as shrink films, cling films, stretch films, sealing films, orientation films, snack packaging, heavy-duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, and membranes in food-contact and non-food-contact applications. Fibers may include melt spinning, solution spinning, and melt blown fiber operations for use in woven or non-woven forms to manufacture filters, diaper fabrics, medical clothing, and geotextiles. Extruded articles may include medical tubing, wire and cable coatings, pipes, geomembranes, and pond liners. Molded articles may include single and multi-layered structures in the form of bottles, tanks, large hollow articles, rigid food containers, and toys.

[0100] Test method

[0101] Polymerization activity

[0102] Unless otherwise indicated, all polymerization activities (also expressed as productivity) disclosed in the present invention were measured as the ratio of the polymer produced to the amount of catalyst added to the reactor and are reported as grams of polymer per gram of catalyst per hour (gPE / gcat / hr).

[0103] comonomer content

[0104] Unless otherwise indicated, all comonomer contents disclosed in the present invention (i.e., the amount of comonomer incorporated into the polymer) were measured by rapid FT-IR spectroscopy of the dissolved polymer in gel permeation chromatography (GPC) measurements and reported as weight percentage (weight%). The comonomer content of the polymer is, according to the literature [Lee et al., Toward absolute chemical composition distribution measurement of polyolefins by high-temperature liquid chromatography hyphenated with infrared absorbance and light scattering detectors As described in [86 Anal. Chem. 8649 (2014)], in GPC measurements, the molecular weight of the polymer can be measured by using an infrared detector such as an IR5 detector.

[0105] uptake ratio

[0106] Unless otherwise indicated, all utilization rates disclosed in the present invention are based on the amount of comonomer (e.g., (C3-C)) relative to the amount of monomer unit derived from ethylene. 12 It was measured as the ratio of the amount of monomer units derived from α-olefin comonomers.

[0107] molecular weight

[0108] Unless otherwise indicated, all molecular weights disclosed herein, e.g., weight average molecular weight (M w ), number average molecular weight (M n ), and z-average molecular weight (M z ) was measured using conventional GPC and reported in grams per mole (g / mol).

[0109] The chromatography system consisted of a high-temperature gel permeation chromatograph (Polymer Laboratories) equipped with a differential refractive index detector (DRI). Three Polymer Laboratories PLgel 10 μm Mixed-B columns were used. The nominal flow rate was 1.0 mL / min, and the nominal injection volume was 300 μL. Various transport lines, columns, and the differential refractometer (DRI detector) were contained in an oven maintained at 160°C. The solvent for the experiment was prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was subsequently filtered through a 0.1 μm Teflon filter. The TCB was then degassed using an online degassing device before entering the GPC apparatus.

[0110] The polymer solution was prepared by placing the dry polymer in a glass vial, adding the desired amount of TCB, and heating the mixture at 160°C while shaking continuously for approximately 2 hours. All volumes were measured by gravimetric measurement. Injection concentrations ranged from 0.5 to 2.0 mg / ml, with lower concentrations used for samples with higher molecular weights. Before running each sample, the DRI detector was purged. The flow rate in the device was subsequently increased to 1.0 ml / min, and the DRI was stabilized for 8 hours prior to injecting the first sample. Molecular weight was measured by combining column calibration performed with a series of monodisperse polystyrene (PS) standards with universal calibration relationships. MW was calculated from each elution volume using the following formula:

[0111]

[0112] In the expression, the variable with the subscript "X" represents the test sample, while the variable with the subscript "PS" represents the PS. In this method, and Meanwhile, and It was obtained from published literature. Specifically, a / K is 0.695 / 0.000579 for PE and 0.705 / 0.0002288 for PP.

[0113] At each point on the chromatogram, the concentration, c, was calculated from the baseline-subtracted DRI signal, IDRI, using the following formula:

[0114]

[0115] In the equation, KDRI is a constant determined by correcting DRI, and (dn / dc) is the increase in refractive index for the system. Specifically, dn / dc is 0.109 for polyethylene.

[0116] The mass recovery rate was calculated from the ratio of the integrated area of ​​the concentration chromatography to the injection mass and elution volume, equal to the value obtained by multiplying the pre-determined concentration by the injection loop volume.

[0117] Examples

[0118] The examples include a synthesis procedure for a ligand intermediate, a ligand, and an isolated precatalyst, and a polymerization method comprising the precatalyst (also referred to as a metal-ligand complex). One or more features of the present disclosure are illustrated in reference to the examples as follows:

[0119]

[0120] Synthesis of Metal-Ligand Complex 1 (MLC-1)

[0121]

[0122] In a glove box, MeMgBr (methyl magnesium bromide) (3.00 M, 0.28 mL, 0.84 mmol, 4.2 equivalents) in diethyl ether was added to a -30°C suspension of HfCl4 (64 mg, 0.2 mmol, 1.0 equivalents) in anhydrous toluene (6.0 mL). After stirring the resulting mixture for 10 minutes, a solid ligand (described in International Publication WO 2018 / 022975 A1; 266 mg, 0.2 mmol, 1.0 equivalents) was added as a fraction. After stirring the resulting mixture overnight, the solvent was removed under vacuum to obtain a dark residue, which was extracted with hexane (12 mL). The resulting extract was concentrated to about 2 mL and kept in a freezer for 1 day. Any remaining solvent was drained, and the remaining material was dried under vacuum, which produced a metal-ligand complex (204 mg, yield: 66%) as a white powder:

[0123] 1 H NMR (400 MHz, C6D6) δ 8.64 - 8.60 (m, 2H), 8.42 - 8.38 (m, 2H), 7.67 - 7.47 (m, 8H), 7.45 - 7.39 (m, 2H), 7.26 (d, J = 2.5 Hz, 2H), 7.07 (dd, J = 8.9, 3.1 Hz, 3H), 6.84 - 6.75 (m, 2H), 5.27 - 5.19 (m, 2H), 4.35 (d, J = 14.1 Hz, 2H), 3.29 (d, J = 14.1 Hz, 2H), 1.57 (d, J = 3.5 Hz, 4H), 1.47 (s, 18H), 1.34 - 1.19 (m, 30H), 0.80 (s, 18H), 0.58 - 0.48 (m, 12H), 0.35 - 0.24 (m, 2H), -1.08 (s, 6H).

[0124] 19F{1H} NMR (376 MHz, CDCl3) δ -116.40 (m, 2F).

[0125] Synthesis of Metal-Ligand Complex 2 (MLC-2)

[0126]

[0127] In a glove box, MeMgBr (methyl magnesium bromide) (3 M, 0.28 mL, 0.84 mmol, 4.2 equivalents) in diethyl ether was added to a -30°C suspension of HfCl4 (64 mg, 0.2 mmol, 1.0 equivalents) in anhydrous toluene (6.0 mL). After stirring the resulting mixture for 10 minutes, a solid ligand (previously described for MLC-3; 287 mg, 0.2 mmol, 1.0 equivalents) was added as a fraction. After stirring the resulting mixture overnight, the solvent was removed under vacuum to obtain a dark residue, which was extracted with hexane (15 mL). The resulting extract was concentrated to about 2-3 mL and kept in a freezer for 1 day. Any remaining solvent was drained, and the remaining material was dried under vacuum, which produced a metal-ligand complex (270 mg, yield: 82%) as a white powder:

[0128] 1H NMR (400 MHz, C6D6) δ 8.71 (d, J = 1.9 Hz, 2H), 8.38 (d, J = 1.9 Hz, 2H), 7.69 - 7.59 (m, 6H), 7.49 (dd, J = 11.6, 2.5 Hz, 4H), 7.42 - 7.37 (m, 2H), 7.32 (dd, J = 8.7, 1.8 Hz, 2H), 7.28 - 7.23 (m, 2H), 5.20 (d, J = 8.7 Hz, 2H), 4.14 (d, J = 13.6 Hz, 2H), 3.14 (d, J = 13.6 Hz, 2H), 1.85 - 1.77 (m, 2H), 1.69 - 1.62 (m, 2H), 1.57 (s, 18H), 1.45 - 1.32 (m, 48H), 0.95 (s, 18H), 0.58 (s, 18H), -1.47 (s, 6H).

[0129] Synthesis of Metal-Ligand Complex 3 (MLC-3)

[0130]

[0131] In a glove box, MeMgBr (3 M, 0.11 mL, 0.32 mmol) in diethyl ether was added to a -35°C suspension of HfCl4 (0.026 g, 0.081 mmol) in anhydrous toluene (5 mL). After stirring the resulting mixture for 5 minutes, the ligand (described in U.S. Patent No. 9,029,487; 0.100 g, 0.081 mmol) in toluene (5 mL) was added as a fraction. After stirring the resulting mixture overnight, the solvent was removed under vacuum to obtain a dark residue, which was extracted with a mixture of hexane and toluene (1:1, 10 mL). The resulting extract was filtered and dried under vacuum, yielding a metal-ligand complex (0.089 g, yield: 76%) as a white powder:

[0132] 1H NMR (400 MHz, C6D6): δ 8.44 - 8.33 (m, 2H), 8.10 - 8.03 (m, 2H), 7.69 (d, J = 2.6 Hz, 2H), 7.67 - 7.63 (m, 2H), 7.56 (d, J = 2.6 Hz, 2H), 7.52 - 7.46 (m, 8H), 7.45 - 7.40 (m, 2H), 7.14 - 6.98 (m, 2H), 5.15 (d, J = 8.7 Hz, 2H), 4.30 (d, J = 14.2 Hz, 2H), 3.14 (d, J = 14.3 Hz, 2H), 1.30 (s, 18H), 1.14 (s, 18H), -0.72 (s, 6H), -1.04 (s, 6H).

[0133] Synthesis of Metal-Ligand Complex 4 (MLC-4)

[0134]

[0135] In a glove box, MeMgBr (3 M, 0.23 mL, 0.69 mmol) in diethyl ether was added to a -35°C suspension of HfCl4 (0.055 g, 0.172 mmol) in anhydrous toluene (5 mL). After stirring the resulting mixture for 5 minutes, the ligand (described in International Publication WO 2008 / 033197 A2; 0.150 g, 0.172 mmol) in toluene (5 mL) was added as a fraction. After stirring the resulting mixture overnight, the solvent was removed under vacuum to obtain a dark residue, which was extracted with a mixture of hexane and toluene (1:1, 10 mL). The resulting extract was filtered and dried under vacuum, yielding a metal-ligand complex (0.185 g, yield: 100%) as a white powder:

[0136] 1 H NMR (400 MHz, benzene- d 6): δ 8.37 - 8.29 (m, 2H), 8.09 (dt, J = 7.6, 1.0 Hz, 2H), 7.61 - 7.55 (m, 2H), 7.53 (dd,J = 8.3, 0.9 Hz, 2H), 7.44 (ddd, J = 8.2, 7.1, 1.4 Hz, 2H), 7.38 (td, J = 7.4, 1.1 Hz, 2H), 7.24 (ddd, J = 8.3, 7.1, 1.3 Hz, 2H), 7.14 - 7.09 (m, 4H), 7.04 - 6.98 (m, 4H), 6.73 (dd, J = 8.4, 2.3 Hz, 2H), 5.02 (d, J = 8.3 Hz, 2H), 4.36 (d, J = 14.2 Hz, 2H), 3.19 (d, J = 14.2 Hz, 2H), 2.16 (s, 6H), 1.97 (s, 6H), 0.37 (t, J = 8.0 Hz, 6H), -0.01 - -0.27 (m, 4H), -1.09 (s, 6H).

[0137] Synthesis of Metal-Ligand Complex 5 (MLC-5)

[0138]

[0139] 글러브박스에서, 디- tButylsilyl detriplate (4.41 g, 10.0 mmol, 1.0 equivalent) was dissolved in anhydrous THF (50 mL) in a 250 mL single-neck round-bottom flask. The flask was capped with a diaphragm, sealed, removed from a glove box, and cooled to -78°C in a dry ice-acetone bath, after which bromochloromethane (1.95 mL, 30 mmol, 3.0 equivalent) was added. Next, a solution of n-BuLi (9.2 mL, 23.0 mmol, 2.3 equivalent) in hexane was added to the cooled wall of the flask over a period of 3 hours using a syringe pump. The resulting mixture was heated to room temperature overnight (about 16 hours), after which saturated NH4Cl (30 mL) was added. The two resulting layers were separated, and the aqueous layer was extracted with ether (2 x 50 mL). The combined organic layer was dried with MgSO4, filtered, and concentrated under reduced pressure. The unrefined product was used in the next step without further purification.

[0140] In the glove box, 40 mL vial bis(chloromethyl)di- t --Butylsilane (1.21 g, 5.0 mmol, 1.0 equivalent), 4- t The mixture was packed with β-butyl-2-bromophenol (4.6 g, 20.0 mmol, 4.0 equivalents), K3PO4 (6.39 g, 30.0 mmol, 6.0 equivalents), and DMF (5 mL), and the reaction mixture was stirred overnight at 110°C. After cooling to room temperature, the reaction mixture was purified by column chromatography using ether / hexane (0 / 100 - 30 / 70) as the eluent, which is bis((2-bromo-4- t -butylphenoxy)methyl)di- t -Butylsilane (2.6 g, yield: 83%) was produced as a colorless oil:

[0141] 1H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 2.4 Hz, 2H), 7.28 (dd, J = 8.6, 2.4 Hz, 2H), 7.00 (d, J = 8.7 Hz, 2H), 3.96 (s, 4H), 1.29 (s, 18H), 1.22 (s, 18H).

[0142]

[0143] In a glove box, a 40 mL vial equipped with a stirring bar is ((2-bromo-4- t -butylphenoxy)methyl)di- t -Butylsilane (0.46 g, 0.73 mmol, 1.0 equivalent), 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentane-2-yl)phenyl)-9H-carbazole (1.53 g, 2.2 mmol, 3.0 equivalent), t Bu3P Pd G2 (0.011 g, 0.022 mmol, 0.03 equivalents), THF (2 mL), and NaOH (4 M, 1.1 mL, 4.4 mmol, 6.0 equivalents) were packed. The vial was heated under nitrogen at 55°C for 2 hours. Upon completion, the upper organic layer was extracted with ether, filtered through a short plug of silica gel, and the solvent was removed under reduced pressure. The resulting residue was dissolved in THF (10 mL) and MeOH (10 mL). Concentrated HCl (0.5 mL) was subsequently added. The resulting mixture was heated at 75°C for 2 hours and then cooled to room temperature. The solvent was subsequently removed under reduced pressure, and the resulting residue was purified by reverse-phase column chromatography using THF / MeCN (0 / 100 > 100 / 0) as the eluent, which is 6',6'''-(((di- t -butylsilanediyl)bis(methylene))bis(oxy))bis(3-(3,6-di- t-butyl-9H-carbazole-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)(0.71 g, yield: 67%) was produced as a white solid:

[0144] 1 H NMR (400 MHz, CDCl3) δ 8.44 - 8.07 (m, 6H), 7.59 - 7.45 (m, 2H), 7.23 - 7.11 (m, 4H), 6.99 - 6.69 (m, 6H), 6.53 - 6.38 (m, 2H), 5.26 - 5.16 (m, 4H), 3.81 (br s, 2H), 3.19 (br s, 2H), 1.60 - 1.05 (m, 70H), 0.85 (s, 18H), 0.74 (s, 18H).

[0145]

[0146] In a glove box, MeMgBr (methyl magnesium bromide) (3 M, 0.28 mL, 0.84 mmol, 4.2 equivalents) in diethyl ether was added to a -30°C suspension of ZrCl4 (47 mg, 0.2 mmol, 1.0 equivalent) in anhydrous toluene (6.0 mL). After stirring the resulting mixture for 2 minutes, the solid 6',6'''-(((di- t -butylsilanediyl)bis(methylene))bis(oxy))bis(3-(3,6-di- t -butyl-9H-carbazole-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol) (287 mg, 0.2 mmol, 1.0 equivalent) was added as a fraction. The resulting mixture was stirred overnight, after which the solvent was removed under vacuum to obtain a dark residue, which was extracted with hexane (15 mL). The resulting extract was concentrated to about 2-3 mL and placed in a freezer for 1 day. Any remaining solvent was decanted, and the remaining material was dried under vacuum, yielding a metal-ligand complex (250 mg, yield: 80%) as a white powder:

[0147] 1 H NMR (400 MHz, C6D6) δ 8.71 (d, J = 1.7 Hz, 2H), 8.38 (d, J = 1.7 Hz, 2H), 7.68 - 7.59 (m, 6H), 7.52 - 7.42 (m, 6H), 7.34 (s, 2H), 7.33 (dd, J = 8.7, 1.9 Hz, 2H), 7.24 (dd, J = 8.7, 2.6 Hz, 2H), 5.17 (d, J = 8.7 Hz, 2H), 4.05 (d, J = 13.5 Hz, 2H), 3.08 (d, J = 13.5 Hz, 2H), 1.85 - 1.77 (m, 2H), 1.70 - 1.62 (m, 2H), 1.57 (s, 18H), 1.45 - 1.32 (m, 48H), 0.95 (s, 18H), 0.59 (s, 18H), -1.22 (s, 6H).

[0148] Synthesis of Metal-Ligand Complex 6 (MLC-6)

[0149]

[0150] In a glove box, diisopropyldichlorosilane (3.703 g, 20 mmol, 1.0 equivalent) was dissolved in anhydrous THF (120 mL) in a 250 mL single-neck round-bottom flask. The flask was capped with a diaphragm, sealed, removed from the glove box, and cooled to -78°C in a dry ice-acetone bath, after which bromochloromethane (3.9 mL, 60 mmol, 3.0 equivalent) was added. Next, a solution of n-BuLi (18.4 mL, 46 mmol, 2.3 equivalent) in hexane was added to the cooled wall of the flask over a period of 3 hours using a syringe pump. After warming the mixture to room temperature overnight (about 16 hours), saturated NH4Cl (30 mL) was added. The resulting two layers were separated, and the aqueous layer was extracted with ether (2 x 50 mL). The combined organic layer was dried with MgSO4, filtered, and concentrated under reduced pressure. The unrefined product was used in the next step without further purification.

[0151] In a glove box, a 40 mL vial of bis(chloromethyl)diisopropylsilane (2.14 g, 10 mmol, 1.0 equivalent), 4- t The mixture was packed with β-butyl-2-bromophenol (6.21 g, 27 mmol, 2.7 equivalents), K3PO4 (7.46 g, 35 mmol, 3.5 equivalents), and DMF (10 mL), and the reaction mixture was stirred overnight at 80°C. After cooling to room temperature, the reaction mixture was purified by column chromatography using ether / hexane (0 / 100 > 30 / 70) as the eluent, which was bis((2-bromo-4- t -Butylphenoxy)methyl)diisopropylsilane (4.4 g, yield: 73%) was produced as a colorless oil:

[0152] 1 H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 2.4 Hz, 2H), 7.26 (dd, J = 8.6, 2.4 Hz, 2H), 6.98 (d, J = 8.6 Hz, 2H), 3.93 (s, 4H), 1.45 - 1.33 (m, 2H), 1.28 (s, 18H), 1.20 (d, J = 7.3 Hz, 12H).

[0153]

[0154] In a glove box, a 40 mL vial equipped with a stirring bar is ((2-bromo-4- tThe vial was filled with 2-(3',5'-di-tert-butyl-5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.54 g, 5.0 mmol, 2.5 equivalents), tBu3P Pd G2 (0.031 g, 0.06 mmol, 0.03 equivalents), THF (3 mL), and NaOH (4 M, 3.0 mL, 12.0 mmol, 6.0 equivalents). The vial was heated under nitrogen at 55°C for 2 hours. Upon completion, the upper organic layer was extracted with ether, filtered through a short plug of silica gel, and the solvent was removed under reduced pressure. The resulting residue was dissolved in THF (10 mL) and MeOH (10 mL). Concentrated HCl (0.5 mL) was subsequently added, and the resulting mixture was heated at 75°C for 2 hours, followed by cooling to room temperature. The solvent was then removed under reduced pressure, and the resulting residue was purified by reverse-phase column chromatography using THF / MeCN (0 / 100 > 100 / 0) as the eluent, yielding 6",6""'-(((diisopropylsilanediyl)bis(methylene))bis(oxy))bis(3,3",5-tri-tert-butyl-5'-methyl-[1,1':3',1"-terphenyl]-2'-ol) (1.62 g, yield: 78%) as a white solid:

[0155] 1H NMR (400 MHz, CDCl3) δ 7.39 (t, J = 1.8 Hz, 2H), 7.36 (d, J = 1.8 Hz, 4H), 7.29 (d, J = 2.5 Hz, 2H), 7.22 (dd, J = 8.6, 2.6 Hz, 2H), 7.10 (d, J = 2.2 Hz, 2H), 6.94 (d, J = 2.3, 2H), 6.75 (d, J = 8.6 Hz, 2H), 5.37 (s, 2H), 3.61 (s, 4H), 2.32 (d, J = 0.9 Hz, 6H), 1.33 (s, 36H), 1.29 (s, 18H), 0.90 - 0.81 (m, 2H), 0.73 (d, J = 7.1 Hz, 12H).

[0156]

[0157] In a glove box, MeMgBr (3.00 M, 0.29 mL, 0.86 mmol, 4.3 equivalents) in diethyl ether was added to a -30°C suspension of ZrCl4 (47 mg, 0.2 mmol, 1.0 equivalents) in anhydrous toluene (6.0 mL). After stirring for 2 minutes, 6",6""'-(((diisopropylsilanediyl)bis(methylene))bis(oxy))bis(3,3",5-tri-tert-butyl-5'-methyl-[1,1':3',1"-terphenyl]-2'-ol) (206 mg, 0.2 mmol, 1.0 equivalent) was added as a fraction. After stirring the resulting mixture overnight at room temperature, the solvent was removed under vacuum to obtain a dark residue, which was washed with hexane (10 mL) and extracted with toluene (12 mL). After filtration, the toluene extract was dried under vacuum, yielding a metal-ligand complex (170 mg, yield: 74%) as a white solid:

[0158] 1H NMR (400 MHz, C6D6) δ 8.20 - 7.67 (m, 4H), 7.79 (t, J = 1.8 Hz, 2H), 7.56 (d, J = 2.5 Hz, 2H), 7.26 (d, J = 2.4, 2H), 7.21 (d, J = 2.4, 2H), 7.18 (d, J = 2.4, 2H), 5.67 (d, J = 8.6 Hz, 2H), 4.61 (d, J = 13.5 Hz, 2H), 3.46 (d, J = 13.5 Hz, 2H), 2.26 (s, 6H), 1.47 (s, 36H), 1.25 (s, 18H), 0.52 (dd, J = 17.0, 7.5 Hz, 12H), 0.30 - 0.18 (m, 2H), - 0.05 (s, 6H).

[0159] Synthesis of Metal-Ligand Complex 7 (MLC-7)

[0160]

[0161] In a glove box, a 40 mL vial equipped with a stirring bar is ((2-bromo-4- t -butylphenoxy)methyl)di- t -Butylsilane (0.5 g, 0.80 mmol, 1.0 equivalent), 2-(3',5'-di-tert-butyl-5-methyl-2-((tetrahydro-2H-pyran-2-yl)oxy)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.21 g, 2.40 mmol, 3.0 equivalent), tBu3P Pd G2 (0.012 g, 0.024 mmol, 0.03 equivalents), THF (2 mL), and KOH (4 M, 1.2 mL, 4.8 mmol, 6.0 equivalents) were packed. The vial was heated under nitrogen at 55°C for 2 hours. Upon completion, the upper organic layer was extracted with ether, filtered through a short plug of silica gel, and the solvent was removed under reduced pressure. The resulting residue was dissolved in THF (10 mL) and MeOH (10 mL). Concentrated HCl (0.5 mL) was subsequently added. The resulting mixture was heated at 75°C for 2 hours and then cooled to room temperature. The solvent was subsequently removed under reduced pressure, and the resulting residue was purified by reverse-phase column chromatography using THF / MeCN (0 / 100 > 100 / 0) as the eluent, which is 6",6""'-(((di- t -butylsilanediyl)bis(methylene))bis(oxy))bis(3,3",5-tri-tert-butyl-5'-methyl-[1,1':3',1"-terphenyl]-2'-ol) (0.63 g, yield: 75%) was produced as a white solid:

[0162] 1 H NMR (400 MHz, CDCl3) δ 7.39 - 7.37 (m, 2H), 7.36 - 7.34 (m, 2H), 7.25 - 7.22 (m, 2H), 7.10 (d, J = 2.4 Hz, 2H), 6.93 (d, J = 2.3, 2H), 6.83 (d, J = 8.2, 2H), 5.13 (s, 2H), 3.63 (s, 4H), 2.32 (s, 6H), 1.32 (s, 36H), 1.28 (s, 18H), 0.78 (s, 18H).

[0163] In a glove box, MeMgBr (3 M, 0.281 mL, 0.86 mmol, 4.3 equivalents) in diethyl ether was added to a -30°C suspension of ZrCl4 (0.046 g, 0.2 mmol, 1.0 equivalent) in anhydrous toluene (6 mL). After stirring the resulting mixture for 2 minutes, the solid 6",6""'-(((di- t -butylsilanediyl)bis(methylene))bis(oxy))bis(3,3",5-tri-tert-butyl-5'-methyl-[1,1':3',1"-terphenyl]-2'-ol) (0.212 g, 0.2 mmol, 1.0 equivalent) was added as a fraction. The resulting mixture was rinsed with toluene (2 mL) and stirred overnight; afterward, the solvent was removed under vacuum to obtain a dark residue, which was washed with hexane (10 mL), filtered, and extracted with toluene (15 mL). The resulting extract was dried under vacuum, yielding a metal-ligand complex (0.2 g, yield: 85%) as a white powder:

[0164] 1 H NMR (400 MHz, C6D6) δ 7.93 (br s, 2H), 7.79 (t, J = 1.9 Hz, 2H), 7.65 (br s, 2H), 7.63 (d, J = 2.5 Hz, 2H), 7.23 - 7.17 (m, 4H), 7.04 - 6.98 (m, 2H), 5.92 (d, J = 8.6 Hz, 2H), 4.56 (d, J = 13.3 Hz, 2H), 3.45 (d, J = 13.2 Hz, 2H), 2.25 (s, 6H), 1.69 - 1.32 (m, 36H), 1.28 (s, 18H), 0.52 (s, 18H), -0.18 (s, 6H).

[0165] Preparation of the spray-dried effective catalyst of the present invention:

[0166] Manufacturing of catalytic systems

[0167] Various catalyst systems were produced by spray drying. Specifically, fuming silica (commercially available as CAB-O-SIL® from Cabot Corporation) and methylaluminoxane (10 wt% in toluene) were dissolved in toluene and mixed for 15 minutes. A metal-ligand complex was added to the resulting slurry and mixed for an additional 30 to 60 minutes. The resulting catalyst system precursor was then dried using a spray dryer (commercially available as Mini Spray Dryer B-290 from BUCHI Corporation) having an inlet temperature of 185°C, an outlet temperature of 100°C, a suction speed of 95 revolutions per minute (rpm), and a pump speed of 150 rpm.

[0168]

[0169] Gas-phase batch reactor test:

[0170] The spray-dried catalyst prepared above was used for ethylene / 1-hexene copolymerization carried out in the gas phase in a 2L semi-batch autoclave polymerization reactor. The individual execution conditions and the characteristics of the polymers produced in these executions are tabled as the tested characteristic results.

[0171] Gas-phase batch reactor catalyst test procedure:

[0172] The gas phase reactor used was a 2-liter stainless steel autoclave equipped with a mechanical stirrer. For the experimental run, the reactor was first dried for 1 hour, charged with 200 g of NaCl, and dried by heating at 100°C under nitrogen for 30 minutes. Following this baking-out process of the reactor, 3 g of SDMAO (supported methylaluminoxane) (only 5 g of SDMAO was used for sd-Cat1) was introduced as a scavenger under nitrogen pressure. After adding SDMAO, the reactor was sealed and the components stirred. The reactor was then charged with hydrogen and 1-hexene and pressurized with ethylene. Once the system reached a steady state, the catalyst was charged into the reactor at 80°C to initiate polymerization. The reactor temperature was raised to the desired reaction temperature and maintained at this temperature and the ratios of ethylene, 1-hexene, and hydrogen throughout the 1-hour run. At the end of the run, the reactor was cooled, vented, and opened. The resulting product mixture was washed with water and methanol and then dried. Polymerization productivity (g polymer / g catalyst-time) was measured as the ratio of the polymer produced to the amount of catalyst added to the reactor.

[0173] manufacturing of polyethylene

[0174] The reaction conditions used for each run are reported in Tables 2, 4, and 6. Reactor data for each run are reported in Table 4. The poly(ethylene- produced by each run nose The characteristics of -1-hexene copolymers (ethylene copolymers) are reported in Tables 3, 5, and 7.

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181] Polymers with an increase in weight percentage (wt%) of comonomers as a function of the molecular weight (MW) of the polymer chain exhibit improved performance in many applications. This is also represented by polymers having a broad orthogonal compositional distribution (BOCD). Quantitatively, the measure of "reverse-ness" or "BOCD-ness" is the Molecular Weight Comonomer Distribution Index (MWCDI). A polymer is said to be BOCD or have a reverse comonomer distribution if its MWCDI is greater than 0, while a polymer with an MWCDI less than 0 is said to have a normal (or Ziegler-Natta) type comonomer distribution, and a polymer with an MWCDI of 0 is said to have a flat comonomer distribution. Specific polymer properties typically improve as the comonomer distribution shifts in reverse from normal to flat.

[0182] Table 3 indicates that the ethylene copolymers of Examples 1 to 5, prepared with spray-dried catalyst sd-IC-1 in a gas-phase polymerization batch reactor, have inverse comonomer distributions and unimodal molecular weight distributions. The molecular weight distribution (MWD) and MWCDI were measured by conventional GPC analysis as previously described. The molecular weight comonomer distribution index (MWCDI) and molecular weight distribution (MWD) of Examples 1 and 4 of the present invention are graphed in Fig. 1; Example 12 in Table 4 is shown in Fig. 2; Example 13 in Table 4 is shown in Fig. 3; and Examples 15 and 16 are shown in Fig. 4. Figs. 1 to 4 also indicate that the ethylene copolymers are unimodal based on a single maximum of the MWD curve. In addition, as shown in FIGS. 1 to 4, the MWCDI line has a slope greater than 0, indicating that there is reverse comonomer incorporation.

Claims

Claim 1 Reactor temperature of 60°C to 150°C or lower and one or more (C3-C) for ethylene 12 ethylene and one or more (C3-C) α-olefin comonomers in the presence of a catalyst system in a single gas-phase polymerization reactor at a molar feed ratio of 0.020 or less. 12 A method for producing an ethylene-based copolymer having a reverse comonomer distribution, comprising polymerizing an α-olefin comonomer, wherein the catalyst system comprises one or more support materials and an active metal-ligand complex having a structure according to the following chemical formula (Ia): Among the formulas: A - is an anion; M is titanium, zirconium, or hafnium; n is 1, 2, or 3; each X is independently unsaturated (C2-C 50 )hydrocarbon, unsaturated (C2-C 50 )heterohydrocarbon, (C1-C 50 )hydrocarville, (C1-C 50 )heterohydrocarbyl, ( C6-C 50 )aryl, ( C4-C 50 )heteroaryl, halogen, -N(R N )2, and -N(R N )COR C It is a monolocate ligand selected from; each Z is independently -O-, -S-, (C6-C 50 )aryl, ( C4-C 50 )heteroaryl, N(C1-C 40 )hydrocarbyl, and P(C1-C 40 )Selected from hydrocarbyl;R 1 and R 16 is independently (C6-C 50 )aryl, ( C4-C 50 )heteroaryl, (C1-C 40 )alkyl, (C3-C 40 ) Selected from heteroalkyl, radical having the following formula (II), radical having the following formula (III), and radical having the following formula (IV): Here, R 31-35 , R 41-48 , and R 51-59 is independently -H, (C1-C 50 )hydrocarville, (C1-C 50 )heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or selected from halogen;R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 is independently -H, (C1-C 50 )hydrocarville, (C1-C 50 )heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, and selected from halogens;R 17 and R 18 is independently -(CR C 2) m Selected from, where subscript m is 1 to 10;R 19 and R 20 is independently linear or branched (C1-C 20 Selected from )alkyl; each R C , R P , and R N is independently -H, (C1-C 50 )hydrocarbyl, and (C1-C 50 A method in which an ethylene copolymer selected from heterohydrocarbyl has a unimodal molecular weight distribution measured by gel permeation chromatography (GPC) and a molecular weight comonomer distribution index greater than 0 measured by rapid Fourier Transform-Infrared (FT-IR) spectroscopy for the copolymer dissolved during gel permeation chromatography (GPC) measurement. Claim 2 In paragraph 1, R 1 and R 16 This same method. Claim 3 In paragraph 1 or 2, R 1 and R 16 At least one of them is a radical having the chemical formula (II) and R 32 and R 34 At least one of them tert -Butyl phosphorus, method. Claim 4 In paragraph 1 or 2, R 1 and R 16 A method in which at least one of the radicals has the chemical formula (III). Claim 5 ◈Claim 5 was waived upon payment of the establishment registration fee.◈ In Paragraph 4, R 42 , R 43 , R 46 , and R 47 At least one of them tert -Butyl phosphorus, method. Claim 6 ◈Claim 6 was waived upon payment of the establishment registration fee.◈ In Paragraph 4, R 41-48 This -H method. Claim 7 ◈Claim 7 was abandoned upon payment of the registration fee.◈ The method of Claim 1 or 2, wherein one or more supporting materials comprise fuming silica. Claim 8 ◈Claim 8 was abandoned upon payment of the registration fee.◈ The method of Claim 1 or 2, wherein the catalyst system comprises spray-dried particles. Claim 9 ◈Claim 9 was abandoned upon payment of the registration fee.◈ A method according to Claim 1 or 2 for producing 2,500 grams or more of an ethylene-based copolymer per gram of catalyst per hour. Claim 10 ◈Claim 10 was abandoned upon payment of the registration fee.◈ A method according to Claim 1 or 2, wherein the ratio of the weight-average molecular weight of the ethylene copolymer to the weight percentage comonomer content of the ethylene copolymer is 10,000 or more; the ratio of the weight-average molecular weight of the ethylene copolymer to the weight percentage comonomer content of the ethylene copolymer is 20,000 or more; or the ratio of the weight-average molecular weight of the ethylene copolymer to the weight percentage comonomer content of the ethylene copolymer is 30,000 or more. Claim 11 Reactor temperature of 150℃ or lower and one or more (C3-C) for ethylene 12 ethylene and one or more (C3-C) α-olefin comonomers in the presence of a catalyst system in a single gas-phase polymerization reactor at a molar feed ratio of 0.020 or less. 12 A method for producing an ethylene-based copolymer having a reverse comonomer distribution, comprising polymerizing an α-olefin comonomer, wherein the catalyst system comprises an activated metal-ligand complex having a group IV metal center, at least one dianionic heterohydrocarbyl ligand, and one or more monoanionic hydrocarbyl ligands, wherein the monoligand is not cyclopentadienyl; the catalyst system does not contain a support material; and the ethylene-based copolymer has a unimodal molecular weight distribution and a molecular weight comonomer distribution index greater than zero. Claim 12 ◈Claim 12 was abandoned upon payment of the registration fee.◈ The method of Claim 1 or 11, wherein the catalyst system additionally comprises one or more activators. Claim 13 ◈Claim 13 was abandoned upon payment of the registration fee.◈ The method of Claim 12, wherein one or more activators comprise methylalumonic acid (MAO). Claim 14 ◈Claim 14 was abandoned upon payment of the registration fee.◈ The method of Claim 1 or 11, wherein the catalyst system is supplied to a gas-phase polymerization reactor in a pure form, as a solution, as a slurry, or a combination thereof. Claim 15 ◈Claim 15 was abandoned upon payment of the registration fee.◈ The method of Claim 1 or 11, wherein the reactor temperature is 120°C or lower; the reactor temperature is 75°C to 105°C; the reactor temperature is 80°C to 100°C; or the reactor temperature is 85°C to 95°C. Claim 16 ◈Claim 16 was abandoned upon payment of the registration fee.◈ The method of Claim 1 or 11, wherein the molecular weight of the ethylene copolymer is greater than 200,000 g / mol; or the ethylene copolymer comprises a molecular weight greater than 500,000 g / mol. Claim 17 ◈Claim 17 was abandoned upon payment of the registration fee.◈ Method according to Claim 1 or 11, wherein the ethylene copolymer further comprises less than 30 weight% of comonomer incorporation as measured by rapid FT-IR spectroscopy of the dissolved polymer by GPC measurement.

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