Supported amidine complexes bearing 4-amino-benzimidazole ligands for making poly(ethylene-co-1-alkene) in a slurry-phase polymerization reactor

Abstract

Supported catalyst systems comprising a support, an activator, and a metal–ligand complex having a structure according to Formula (I), where: M is titanium, zirconium, or hafnium; each X is a monodentate or bidentate ligand; n is 0, 1, or 2; each of R1 and R5 is independently selected from the group consisting of (C1–‍C30)hydrocarbyl, (C1–‍C30)heterohydrocarbyl, (C6–‍C30)aryl, and (C3–‍C30)heteroaryl; each of R2, R3, R4, and R6 is independently selected from the group consisting of (C1–‍C30)hydrocarbyl, (C1–‍C30)heterohydrocarbyl, (C6–‍C30)aryl, (C3–‍C30)heteroaryl, −ORC, ‍−Si(RC)3, −Ge(RC)3, halogen, and –H; each of Sub1 and Sub2 is independently selected from the group consisting of (C1–‍C30)hydrocarbyl, (C1–‍C30)heterohydrocarbyl, (C6–‍C30)aryl, and (C3–‍C30)heteroaryl, −ORC, −N(RC)2, −Si(RC)3, −Ge(RC)3, and –H; and each RC is independently selected from the group consisting of (C1–‍C30)hydrocarbyl, (C1–‍C30)heterohydrocarbyl, (C6–‍C30)aryl, (C3–‍C30)heteroaryl, and −H.

Description

86409-WO-PCT / DOW 86409 WO1SUPPORTED AMIDINE COMPLEXES BEARING 4-AMINO-BENZIMIDAZOLE LIGANDS FOR MAKING POLY(ETHYLENE-CO-1-ALKENE) IN A SLURRY-PHASE POLYMERIZATION REACTORCROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U. S. Provisional Application Serial No. 63 / 765,177 filed February 28, 2025, the entire disclosure of which is hereby incorporated by reference.TECHNICAL FIELD

[0002] Embodiments of the present disclosure are generally directed to catalyst systems for olefin polymerization and, more specifically, to supported catalyst systems including Group IV transition metal catalysts and olefin polymerization processes incorporating the same.BACKGROUND

[0003] Olefin-based polymers such as polyethylene and ethylene-based polymers are produced via various catalyst systems. Selection of such catalyst systems used in the polymerization process of the olefin-based polymers is an important factor contributing to the characteristics and properties of such olefin-based polymers.

[0004] Ethylene-based polymers are manufactured for a wide variety of articles. The polymerization process for ethylene-based polymers can be varied in a number of respects to produce a wide variety of resultant polymer resins having different physical properties that render the various resins suitable for use in different applications. The ethylene monomers and, optionally, one or more comonomers, are present in liquid diluents (such as solvents), such as an alkane or isoalkane, for example isobutane or Isopar E in a solution polymerization reactor, or are present as gases in a gas-phase polymerization reactor. Hydrogen may also be added to the reactor.

[0005] The catalyst systems for producing ethylene-based polymers typically include a chromium-based catalyst system, a Ziegler-Natta catalyst system, and / or a molecular (either metallocene or non-metallocene) catalyst system. The reactants and the catalyst system are circulated at an elevated polymerization temperature around the reactor, thereby producing ethylene-based homopolymer or copolymer. Either periodically or continuously, part of the reaction mixture, including ethylene-based polymer product dissolved in the diluent, together with unreacted ethylene and one or more optional comonomers, is removed from the reactor. The reaction mixture, when removed from the reactor, may be processed to remove the ethylene-based polymer product from the86409-WO-PCT / DOW 86409 WO2diluent and the unreacted reactants, with the diluent and unreacted reactants typically being recycled back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor, serially connected to the first reactor, where a second polyethylene fraction may be produced.SUMMARY

[0006] Despite previous research efforts in developing catalyst systems suitable for olefin polymerization, such as the polymerization of ethylene-based polymers, there is still a need to develop supported catalyst systems with advantageous productivity, efficiency, operability, and resultant polymer properties relative to commercial incumbent catalyst systems. For example, supported catalyst systems for the efficient production of high molecular weight poly(ethylene-co-l -alkene) copolymers with low comonomer incorporation compared to commercial incumbents are of particular interest to the slurry-phase and gas-phase polyethylene industries for single and multi-catalyst systems under commercially relevant high and low density process conditions. Further, a combination of lower comonomer incorporation, high weight-average molecular weight Mw, and similar-to-higher activity at lower reactor temperatures will allow for the production of polymers with improved product performance in linear low-to-high density polyethylene applications as well as additional process flexibility in the production of poly(ethylene-co-l -alkene) copolymers.

[0007] It has now been discovered that supported catalyst systems employing Group IV heteroleptic amidine complexes bearing a 4-amino-benzimidazole ligand have high activity under commercially relevant process conditions at higher (100 °C) and lower (80 °C) reactor temperatures and are capable of producing poly(ethylene-co-l -alkene) copolymers with low comonomer incorporation (e.g., less than 0.5 wt% comonomer) and high weight-average molecular weight (e.g., greater than 800,000 g / mol). The high activity at lower reactor temperatures exhibited by the supported catalyst systems described herein is advantageous in some gas-phase polymerization processes. In addition to high activity, some of the poly(ethylene-co-l -alkene) copolymers produced using the catalyst systems described herein have high Mwand ultra-low comonomer incorporation, which shows that the catalyst systems may be amenable to making bi- and multi-modal resins with larger, improved comonomer deltas and additional degrees of freedom in the catalyst options for differentiated resin / product designs, which can improve the end resin / product performance. Currently, this capability, under process relevant conditions in combination with high productivity and efficiency is of high interest for the development of catalysts for use in gas-phase and slurry-phase polymerization processes.86409-WO-PCT / DOW 86409 WO3

[0008] Embodiments of this disclosure include supported catalyst systems comprising heteroleptic 4-amino-benzimidazole amidine complexes, and methods of making a poly(ethylene-co-1-alkene) copolymer that include polymerizing, via gas-phase polymerization or slurry -phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of the supported catalyst systems disclosed herein.

[0009] According to a first aspect of the present disclosure, a supported catalyst system comprises a support, an activator, and a metal-ligand complex having a structure according to Formula (I):

[0010] In Formula (I): M is a metal selected from the group consisting of titanium, zirconium, and hafnium, the metal having a formal oxidation state of +2, +3, or +4; each X is a monodentate or bidentate ligand independently selected from the group consisting of unsaturated (C2-C3o)hydrocarbon, unsaturated (C2-C3o)heterohydrocarbon, (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, halogen, -N(RX)2, and -(CH2)wSi(Rx)3, where w is 1 to 10 and each Rxis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl; n is 0, 1, or 2; each of R1and R5is independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl; each of R2, R3, R4, and R6is independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H; each of Subi and Sub2 is independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl, -ORC, -N(RC)2, -Si(Rc)3, -Ge(Rc)3, and -H, wherein Subi and Sub2 are optionally covalently connected to form an aromatic ring, a non-aromatic ring, or a multi-ring structure; and each Rcis independently86409-WO-PCT / DOW 86409 WO4selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6-C3o)aryl, (C3-C3o)heteroaryl, and -H.

[0011] A second aspect includes the first aspect, wherein: M is zirconium or hafnium; each X is independently selected from the group consisting of (Ci-Cio)alkyl, (Ce-C2o)aryl, -(CH2)wSi(Rx)3, and halogen; and R1is (Ci-C3o)alkyl or (Ce-C3o)aryl.

[0012] A third aspect includes either one of the first or second aspects, wherein M is zirconium.

[0013] A fourth aspect includes any one of the first through third aspects, wherein R1is (C6-C3o)aryl.

[0014] A fifth aspect includes any one of the first through fourth aspects, wherein R1is unsubstituted phenyl or substituted phenyl.

[0015] A sixth aspect includes any one of the first through fifth aspects, wherein R1is substituted phenyl containing at least two (Ci-Cio)alkyl substituents.

[0016] A seventh aspect includes the sixth aspect, wherein the at least two (Ci-Cio)alkyl substituents comprise two (Ci-Cio)alkyl / 7 / z -substituents.

[0017] An eighth aspect includes any one of the first through seventh aspects, wherein R1is 2,6-dimethylphenyl or 2,6-di(iso-propyl)phenyl.

[0018] A ninth aspect includes any one of the first through fifth aspects, wherein R1is 2-methylphenyl, 2,6-dimethylphenyl, or 2,6-di(iso-propyl)phenyl.

[0019] A tenth aspect includes any one of the first through ninth aspects, wherein R6is (C6-C2o)aryl or (C3-C2o)cycloalkyl.

[0020] An eleventh aspect includes any one of the first through tenth aspects, wherein R6is unsubstituted phenyl or substituted phenyl.

[0021] A twelfth aspect includes any one of the first through eleventh aspects, wherein R6is 2-methylphenyl.

[0022] A thirteenth aspect includes any one of the first through twelfth aspects, wherein R5is (Ci-Cio)alkyl or (Ce-C2o)aryl.

[0023] A fourteenth aspect includes any one of the first through thirteenth aspects, wherein R5is 4-butylphenyl.86409-WO-PCT / DOW 86409 WO5

[0024] A fifteenth aspect includes any one of the first through fourteenth aspects, wherein R2, R3, and R4are -H.

[0025] A sixteenth aspect includes any one of the first through fifteenth aspects, wherein the metal-ligand complex has a structure according to Formula (II):R8RV, ILR7NM^X)n (II)R6\\ V zN" R1R5R3

[0026] In Formula (II): each of R1–6, X, M, and n are defined as in Formula (I); and each of R7, R8, and R9is independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, and halogen, wherein optionally, any of R7, R8, and R9are covalently connected to form at least one of an aromatic ring, a non-aromatic ring, or a multi-ring structure.

[0027] A seventeenth aspect includes the sixteenth aspect, wherein R7is (Ce-C3o)aryl.

[0028] An eighteenth aspect includes either one of the sixteenth or seventeenth aspects, wherein R7is unsubstituted phenyl or substituted phenyl.

[0029] A nineteenth aspect includes any one of the sixteenth through eighteenth aspects, wherein R7is unsubstituted phenyl.

[0030] A twentieth aspect includes any one of the sixteenth through nineteenth aspects, wherein R8and R9are independently (Ci-Cio)alkyl.

[0031] A twenty-first aspect includes any one of the sixteenth through twentieth aspects, wherein R8and R9are isopropyl.86409-WO-PCT / DOW 86409 WO6

[0032] A twenty-second aspect includes any one of the first through twenty-first aspects, wherein each X is independently selected from the group consisting of methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro.

[0033] A twenty -third aspect includes any one of the first through twenty-second aspects, wherein each X is benzyl.

[0034] A twenty-fourth aspect includes any one of the first through fifth or ninth through twenty-third aspects, wherein the metal-ligand complex is selected from the group consisting of IMLC-1, IMLC-2, and IMLC-3:

[0035] A twenty-fifth aspect includes the twenty-fourth aspect, wherein the metal-ligand complex is IMLC-2 or IMLC-3.

[0036] A twenty-sixth aspect includes any one of the first through twenty-fifth aspects, wherein the support comprises silica or fumed silica.

[0037] A twenty-seventh aspect includes any one of the first through twenty-sixth aspects, wherein the activator comprises an aluminoxane.

[0038] According to a twenty-eighth aspect of the present disclosure, a method of making an ethylene-based polymer comprises polymerizing, via gas-phase polymerization or slurry-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of the supported catalyst system of any one of the first through twenty-seventh aspects.86409-WO-PCT / DOW 86409 WO7

[0039] A twenty-ninth aspect includes the twenty-eighth aspect, wherein the polymerizing comprises slurry-phase polymerization.

[0040] A thirtieth aspect includes either one of the twenty-eighth or twenty-ninth aspects, wherein the method comprises polymerizing the combination of ethylene monomer and at least one 1 -alkene comonomer.

[0041] A thirty-first aspect includes the thirtieth aspect, wherein the at least one 1 -alkene comonomer comprises 1 -hexene.

[0042] A thirty-second aspect includes any one of the twenty-eighth through thirty-first aspects, wherein the polymerizing is performed at a polymerization temperature of from 75 °C to 110 °C.

[0043] A thirty-third aspect includes any one of the twenty-eighth through thirty-second aspects, wherein the polymerizing is performed at a polymerization temperature of from 80 °C to 100 °C.

[0044] A thirty-fourth aspect includes any one of the twenty-eighth through thirty-third aspects, wherein the polymerizing is performed in the presence of molecular hydrogen gas (H2).

[0045] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter.DETAILED DESCRIPTION

[0046] Specific embodiments of catalyst systems will now be described. It should be understood that the catalyst systems of this disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure. Rather, embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0047] Common abbreviations are listed below:

[0048] R, Q, M, X and n: as defined above; Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; Cy: cyclohexyl; iPr: z o-propyl; nBu: n-butyl; MeOH: methanol; TMS: tetramethylsilane; DCM or CH2CI2: dichloromethane; DMSO: dimethyl sulfoxide; Hex: hexane; EtOAc: ethyl acetate; EtOH: ethanol; MeMgBr: methylmagnesium bromide; C₆D₆: deuterated benzene or benzene-d₆; CDCl₃: deuterated chloroform; Na2SO4: sodium sulfate; CaH2: calcium hydride; BnMgCl: benzylmagnesium chloride; K2CO3: potassium carbonate; NH4CI: ammonium chloride; I2: iodine;86409-WO-PCT / DOW 86409 WO8N₃SiMe₃ or TMS-N₃: trimethylsilyl azide; ZrBn₄: zirconium(IV) tetrabenzyl; Cy₃PNH: tricyclohexyl-phosphinimine; CpZrBn₃: cyclopentadienylzirconium(IV) tribenzyl; CpZrCl₃: cyclopentadienylzirconium(IV) trichloride; Cy₃PNZrBn₄: tricyclohexyl-phosphinimidezirconium(IV) tribenzyl; (amid-Ph)ZrBn₃: N,N-di-iso-propyl-phenylamidinezirconium(IV) tribenzyl; PPR: parallel pressure reactor; MAO: methylaluminoxane;MMAO: modified methylaluminoxane; TEA: triethylaluminum; GPC: gel permeation chromatography; OBD: optimum bed density; BPR: back pressure regulator; LC: liquid chromatography; RIBS-2 or RIB-II: bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-) amine; NMR: nuclear magnetic resonance; MS: mass spectrometry; HRMS: high-resolution mass spectrometry; RT or r.t.: room temperature; psig: pounds per square inch gauge; g: grams; mmol: millimoles; mL: milliliters; mm: millimeters;M: molar; mM: millimolar; min or mins: minutes; h or hrs: hours; d: days; rpm: revolution per minute.

[0049] The term “spectator ligand” refers to a ligand that occupies a coordination site on the metal center of a metal-ligand complex and influences the reactivity of the metal center, but remains bound and does not de-coordinate from the metal center during the course of polymerization. Spectator ligands are also referred to as “ancillary ligands” and are generally less basic or less easily protonated than ligands that de-coordinate from the metal center during polymerization.

[0050] In this disclosure, a “heteroleptic” metal-ligand complex refers to a metal-ligand complex bearing a spectator ligand and one or more additional ligands that are the same or different from one another. At minimum, a heteroleptic complex contains both a spectator ligand and a ligand that participates in chemical reactions carried out by the metal-ligand complex, such as olefin polymerization, by de-coordinating from the metal center of the metal-ligand complex.

[0051] The term “independently selected” followed by multiple options is used herein to indicate that the individual R groups appearing before the term, such as R1, R2, R3, R4, R5, and Rccan be identical or different, without dependency on the identity of any other group also appearing before the term.

[0052] The term “procatalyst” refers to a compound that has catalytic activity when combined with an activator. As used herein, the term “procatalyst” and “precatalyst” are interchangeable terms. The term “activator” refers to a compound that chemically reacts with a procatalyst in a manner that86409-WO-PCT / DOW 86409 WO9converts the procatalyst to a catalytically active catalyst. As used herein, the term “activating cocatalyst” and “activator” are interchangeable terms.

[0053] When used to describe certain carbon atom- containing chemical groups, a parenthetical expression having the form “(Cx-Cy)” means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, a (Ci-C3o)alkyl is an alkyl group having from 1 to 30 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted by one or more substituents such as Rs. An Rssubstituted version of a chemical group defined using the “(Cx-Cy)” parenthetical may contain more than y carbon atoms depending on the identity of any groups Rs. For example, a “(Ci-C5o)alkyl substituted with exactly one group Rs, where Rsis phenyl (-CeHs)” may contain from 7 to 56 carbon atoms. Thus, in general when a chemical group defined using the “(Cx-Cy)” parenthetical is substituted by one or more carbon atom-containing substituents Rs, the minimum and maximum total number of carbon atoms of the chemical group is determined by adding to both x and y the combined sum of the number of carbon atoms from all of the carbon atom- containing substituents Rs.

[0054] The term “substitution” means that at least one hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., Rs). The term “persubstitution” means that every hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., Rs). The term “polysubstitution” means that at least two, but fewer than all, hydrogen atoms bonded to carbon atoms or heteroatoms of a corresponding unsubstituted compound or functional group are replaced by a substituent. The term “-H” means a hydrogen or hydrogen radical that is covalently bonded to another atom. When describing chemical structures of various compounds, “hydrogen” and “-H” are interchangeable, and unless clearly specified have identical meanings.

[0055] The term “(Ci-C3o)hydrocarbyl” means a hydrocarbon radical of from 1 to 30 carbon atoms and the term “(Ci-C3o)hydrocarbylene” means a hydrocarbon diradical of from 1 to 30 carbon atoms, in which each hydrocarbon radical and each hydrocarbon diradical is aromatic or nonaromatic, saturated or unsaturated, straight chain or branched chain, cyclic (having three carbons or more, and including mono- and poly-cyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and substituted by one or more Rsor unsubstituted. Examples of (Ci-C3o)hydrocarbyl are unsubstituted or substituted (Ci-C3o)alkyl, (C3-C3o)cycloalkyl, (C3-C2o)cycloalkyl-(Ci-86409-WO-PCT / DOW 86409 WO10Cio)alkylene, (Ce-C3o)aryl, or (C6-C2o)aryl-(Ci-Cio)alkylene (such as benzyl (-CH2-C6H5)). Examples of (Ci-C5o)hydrocarbyl are unsubstituted or substituted (Ci-C5o)alkyl, (C3-C5o)cycloalkyl, (C3-C2o)cycloalkyl-(Ci-C2o)alkylene, (Ce-C4o)aryl, or (C6-C2o)aryl-(Ci-C2o)alkylene (such as benzyl (-CH2-C6H5)).

[0056] The term “(Ci-C3o)alkyl” means a saturated straight or branched hydrocarbon radical of from 1 to 30 carbon atoms that is unsubstituted or substituted by one or more Rs. Other alkyl groups (e.g., (Cx-Cy)alkyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs. Examples of unsubstituted (Ci-C3o)alkyl are unsubstituted (Ci-C2o)alkyl; unsubstituted (Ci-Cio)alkyl; unsubstituted (Ci-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. Examples of substituted (Ci-C4o)alkyl are substituted (Ci-C2o)alkyl (such as benzyl (-CH2-C6H5)), substituted (Ci-Cio)alkyl, trifluoromethyl, and [C4s]alkyl. The term “[C45]alkyl” means there is a maximum of 45 carbon atoms in the radical, including substituents, and is, for example, a (C27-C4o)alkyl substituted by one Rs, which is a (Ci-C5)alkyl, respectively. Each (Ci-C5)alkyl may be methyl, trifluoromethyl, ethyl, 1 -propyl, 1 -methylethyl, or 1,1 -dimethylethyl.

[0057] The term “(C6-C3o)aryl” means an unsubstituted or substituted (by one or more Rs) mono-, bi- or tricyclic aromatic hydrocarbon radical of from 6 to 30 carbon atoms, of which at least from 6 to 14 of the carbon atoms are aromatic ring carbon atoms. Other aryl groups (e.g., (Cx-Cy)aryl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs. A monocyclic aromatic hydrocarbon radical includes one aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or non-fused and aromatic or non-aromatic. Examples of unsubstituted (Ce-C3o)aryl include: unsubstituted (Ce-C2o)aryl, unsubstituted (C6-Cis)aryl; 2-(Ci-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (Ce-C3o)aryl include: substituted (Ci-C2o)aryl; substituted (C6-Cis)aryl; 2,4-bis([C2o]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-l-yl.

[0058] The term “(C3-C2o)cycloalkyl” means a saturated cyclic hydrocarbon radical of from 3 to 20 carbon atoms that is unsubstituted or substituted by one or more Rs. Other cycloalkyl groups (e.g.,86409-WO-PCT / DOW 86409 WO11(Cx-Cy)cycloalkyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs. Examples of unsubstituted (C3-C2o)cycloalkyl are unsubstituted (C3-Cio)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3-C2o)cycloalkyl are substituted (C3-Cio)cycloalkyl, cyclopentanon-2-yl, and 1 -fluorocyclohexyl.

[0059] Examples of (Ci-C5o)hydrocarbylene include unsubstituted or substituted (C6-C5o)arylene, (C3-C5o)cycloalkylene, and (Ci-C5o)alkylene (e.g., (Ci-C2o)alkylene). The diradicals may be on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or are spaced apart by one, two, or more than two intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or an a,a>-diradical, and others a 1,2-diradical. The a,a>-diradical is a diradical that has maximum carbon backbone spacing between the radical carbons. Some examples of (C2-C2o)alkylene a,a>-diradicals include ethan-1,2-diyl (i.e. -CH2CH2-), propan- 1,3 -diyl (i.e. -CH2CH2CH2-), 2-methylpropan- 1,3 -diyl (i.e. - CH2CH(CH3)CH2- ). Some examples of (Ce-Csojarylene a,a>-diradicals include phenyl- 1,4-diyl, napthalen-2,6-diyl, or napthalen-3,7-diyl.

[0060] The term “(Ci-Csojalkylene” means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from 1 to 50 carbon atoms that is unsubstituted or substituted by one or more Rs. Other alkylene groups (e.g., (Cx-Cy)alkylene) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs. Examples of unsubstituted (Ci-Csojalkylene are unsubstituted (Ci-C2o)alkylene, including unsubstituted -CH2CH2-, −(CH2)3−, −(CH2)4−, −(CH2)5−, −(CH2)6−, −(CH2)5−, −(CH2)8−, −CH2C*HCH3, and −(CH2)4C*(H)(CH3), in which “C*” denotes a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (Ci-Csojalkylene are substituted (Ci-C2o)alkylene, -CF2-, -C(O)-, and - (CH2)i4C(CH3)2(CH2)s“ (i.e., a 6,6-dimethyl substituted normal- 1,20-eicosylene). Since as mentioned previously two Rsmay be taken together to form a (Ci-Ci8)alkylene, examples of substituted (Ci-Csojalkylene also include l,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3- bis (methylene)bicyclo [2.2.2] octane.

[0061] The term “(Cs-Csojcycloalkylene” means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more Rs. Other86409-WO-PCT / DOW 86409 WO12cycloalkylene groups (e.g., (Cx-Cy)cycloalkylene) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs.

[0062] The term “heteroatom” refers to an atom other than hydrogen or carbon. Examples of groups containing one or more than one heteroatom include O, S, S(O), S(O)2, Si(RC)2, P(RP), N(RN), −N=C(RC)2, −Ge(RC)2−, or −Si(RC)−, where each Rcand each Rpis unsubstituted (Ci-Ci8)hydrocarbyl or -H, and where each RNis unsubstituted (Ci-Ci8)hydrocarbyl. The term “heterohydrocarbon” refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. The term “(Ci-C5o)heterohydrocarbyl” means a heterohydrocarbon radical of from 1 to 50 carbon atoms, and the term “(Ci-C5o)heterohydrocarbylene” means a heterohydrocarbon diradical of from 1 to 50 carbon atoms. The heterohydrocarbon of the (Ci-C5o)heterohydrocarbyl or the (Ci-C5o)heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl may be on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene may be on a single carbon atom or on a single heteroatom. Additionally, one of the two radicals of the diradical may be on a carbon atom and the other radical may be on a different carbon atom; one of the two radicals may be on a carbon atom and the other on a heteroatom; or one of the two radicals may be on a heteroatom and the other radical on a different heteroatom. Each (Ci-C5o)heterohydrocarbyl and (Ci-C5o)heterohydrocarbylene may be unsubstituted or substituted (by one or more Rs), aromatic or nonaromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including mono- and poly-cyclic, fused and non-fused polycyclic), or acyclic. Other heterohydrocarbyl groups (e.g., (Cx-Cy) heterohydrocarbyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs.

[0063] The (Ci-C5o)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (Ci-C5o)heterohydrocarbyl include (Ci-C5o)heteroalkyl, (Ci-C5o)hydrocarbyl-0-, (Ci-C5o)hydrocarbyl-S-, (Ci-C5o)hydrocarbyl-S(0)-, (C1–C50)hydrocarbyl-S(O)2−, (Ci-C5o)hydrocarbyl-Si(Rc)2“, (Ci-C5o)hydrocarbyl-N(RN)-, (Ci-C5o)hydrocarbyl-P(Rp)-, (C2-C5o)heterocycloalkyl, (C2-Ci9)heterocycloalkyl-(Ci-C2o)alkylene, (C3-C2o)cycloalkyl-(Ci-Ci9)heteroalkylene, (C2-Ci9)heterocycloalkyl-(Ci-C2o)heteroalkylene, (Ci-C5o)heteroaryl, (Ci-C i9)heteroaryl-(C i-C2o)alkylene, (Ce-C2o)aryl-(C i-C i9)heteroalkylene, or (C i-C i9)heteroaryl-(C 1-C2o)heteroalkylene.86409-WO-PCT / DOW 86409 WO13

[0064] The (Ci-C3o)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (Ci-C3o)heterohydrocarbyl include (Ci-C3o)heteroalkyl, (Ci-C3o)hydrocarbyl-0-, (Ci-C3o)hydrocarbyl-S-, (Ci-C3o)hydrocarbyl-S(0)-, (C1–C30)hydrocarbyl-S(O)2−, (Ci— C3o)hydrocarbyl-Si(Rc)2-, (Ci-C3o)hydrocarbyl-N(RN)-, (Ci-C3o)hydrocarbyl-P(Rp)-, (C2-C3o)heterocycloalkyl, (C2-C2o)heterocycloalkyl-(Ci-Cio)alkylene, (C3-C2o)cycloalkyl-(Ci-Cio)heteroalkylene, (C2-C2o)heterocycloalkyl-(Ci-Cio)heteroalkylene, (Ci-C3o)heteroaryl, (Ci-C2o)heteroaryl-(Ci-Cio)alkylene, (C6-C2o)aryl-(Ci-Cio)heteroalkylene, or (Ci-C2o)heteroaryl-(Ci-Cio)heteroalkylene.

[0065] The term “(C3-C3o)heteroaryl” means an unsubstituted or substituted (by one or more Rs) mono-, bi-, or tricyclic heteroaromatic hydrocarbon radical of from 3 to 30 total carbon atoms and from 1 to 10 heteroatoms. A monocyclic heteroaromatic hydrocarbon radical includes one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical has two rings; and a tricyclic heteroaromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring or rings of the heteroaromatic radical may be independently fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., (Cx-Cy)heteroaryl generally, such as (C4-Ci2)heteroaryl) are defined in an analogous manner as having from x to y carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or substituted by one or more than one Rs. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered ring or a 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1, 2, or 3; and each heteroatom may be O, S, N, or P.

[0066] Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol-l-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-l-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-l-yl; l,3,4-oxadiazol-2-yl; l,3,4-thiadiazol-2-yl; tetrazol- 1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1 or 2 and the heteroatoms may be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon radicals include pyridine-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical can be a fused 5,6- or 6,6-ring system. Examples of the fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radical are indol-l-yl; and benzimidazole- 1-yl. Examples of the fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin- 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 the fused 5,6,5-ring system is86409-WO-PCT / DOW 86409 WO141,7-dihydropyrrolo[3,2-f]indol-l -yl. An example of the fused 5,6,6-ring system is lH-benzo[f] indol-1-yl. An example of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of the fused 6,6,6-ring system is acrydin-9-yl.

[0067] The term “(Ci-C5o)heteroalkyl” means a saturated straight or branched chain radicals containing one to fifty carbon atoms, or fewer carbon atoms and one or more of the heteroatoms. The term “(Ci-C5o)heteroalkylene” means a saturated straight or branched chain diradicals containing from 1 to 50 carbon atoms and one or more than one heteroatoms. The heteroatoms of the heteroalkyls or the heteroalkylenes may include Si(Rc)3, Ge(Rc)3, Si(Rc)2, Ge(Rc)2, P(Rp)2, P(Rp), N(RN)2, N(RN), N, O, ORC, S, SRC, S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups are unsubstituted or are substituted by one or more Rs.

[0068] Examples of unsubstituted (C2-C4o)heterocycloalkyl include unsubstituted (C2-C2o)heterocycloalkyl, unsubstituted (C2-Cio)heterocycloalkyl, aziridin-l-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-l-yl, tetrahydrothiophen-S, S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0069] The term “multi-ring structure” refers to a polycyclic structure that is fused or non- fused, aromatic (in part or in whole) or non-aromatic, unsubstituted or substituted by one or more Rs, and optionally containing one or more heteroatoms as ring atoms of the polycyclic structure.

[0070] The term “halogen atom” or “halogen” means the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). The term “halide” means the anionic form of the halogen atom: fluoride (F"), chloride (Cl"), bromide (Br ), or iodide (I").

[0071] The term “saturated” means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorous, and carbonsilicon double bonds. Where a saturated chemical group is substituted by one or more substituents Rs, one or more double and / or triple bonds optionally may or may not be present in substituents Rs. The term “unsaturated” means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen, carbonphosphorous, or carbon-silicon double bonds, not including double bonds that may be present in substituents Rs, if any, or in (hetero) aromatic rings, if any.

[0072] Embodiments of the supported catalyst systems described herein include a support, an activator, and a metal-ligand complex having a structure according to Formula (I):86409-WO-PCT / DOW 86409 WO15

[0073] In Formula (I), M is a metal selected from the group consisting of titanium, zirconium, and hafnium, the metal having a formal oxidation state of +2, +3, or +4. n is 0, 1, or 2. Each X is a monodentate or bidentate ligand independently selected from the group consisting of unsaturated (C2-C3o)hydrocarbon, unsaturated (C2-C3o)heterohydrocarbon, (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, halogen, -N(RX)2, and -(CH2)wSi(Rx)3, where w is 1 to 10 and each Rxis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl. Each of R1and R5is independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl. Each of R2, R3, R4, and R6is independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H. Each of Subi and Sub2 is independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl, -ORC, -N(RC)2, -Si(Rc)3, -Ge(Rc)3, and -H, wherein Subi and Sub2 are optionally covalently connected to form an aromatic ring, a non-aromatic ring, or a multi-ring structure. Each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6-C3o)aryl, (C3-C3o)heteroaryl, and -H.

[0074] In some example metal-ligand complexes according to Formula (I), M is zirconium or hafnium; each X is independently selected from the group consisting of (Ci-Cio)alkyl, (Ce-C2o)aryl, -(CH2)wSi(Rx)3, and halogen; and R1is (Ci-C3o)alkyl or (C6-C3o)aryl. In some specific examples, M is zirconium.86409-WO-PCT / DOW 86409 WO16

[0075] In some example metal-ligand complexes according to Formula (I), R1is (Ce-C3o)aryl. In some examples, R1is unsubstituted phenyl or substituted phenyl. In some specific examples, R1is 2-methylphenyl, 2,6-dimethylphenyl, or 2,6-di(iso-propyl)phenyl.

[0076] In some examples, R1is substituted phenyl containing at least two (Ci-Cio)alkyl substituents, wherein the at least two (Ci-Cio)alkyl substituents may comprise two (Ci-Cio)alkyl ortAo-substituents. As is demonstrated by the examples of the present disclosure, it has been unexpectedly found that when R1is substituted phenyl containing at least two (Ci-Cio)alkyl substituents, for example, two (Ci-Cio)alkyl ortAo-substituents, the supported catalysts systems described herein are able to produce poly (ethylene- co- 1 -alkene) copolymers having high Mw(e.g., greater than 800,000 g / mol or greater than 1,200,000 g / mol) and ultra-low comonomer incorporation (e.g., less than or equal to 0.1 wt%), while also achieving high activity under commercially relevant process conditions at higher (100 °C) and lower (80 °C) reactor temperatures. In some specific examples, R1is 2,6-dimethylphenyl or 2,6-di(iso-propyl)phenyl.

[0077] In some example metal-ligand complexes according to Formula (I), R6is (Ce-C2o)aryl or (C3-C2o)cycloalkyl. In some examples, R6is unsubstituted phenyl or substituted phenyl. In some specific examples, R6is 2-methylphenyl.

[0078] In some example metal-ligand complexes according to Formula (I), R5is (Ci-Cio)alkyl or (Ce-C2o)aryl. In some specific examples, R5is 4-butylphenyl.

[0079] In some example metal-ligand complexes according to Formula (I), R2, R3, and R4are -H.

[0080] In some examples of the supported catalyst systems described herein, the metal-ligand complex has a structure according to Formula (II):86409-WO-PCT / DOW 86409 WO17R8R7NM^X)n (II)R6\\ V zN" R1R5R3

[0081] In Formula (II), each of R1–6, X, M, and n are defined as in Formula (I), and each of R7, R8, and R9is independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, and halogen, wherein optionally, any of R7, R8, and R9are covalently connected to form at least one of an aromatic ring, a non-aromatic ring, or a multi-ring structure.

[0082] In some example metal-ligand complexes according to Formula (II), R7is (Ce-C3o)aryl. In some examples, R7is unsubstituted phenyl or substituted phenyl. In some specific examples, R7is unsubstituted phenyl.

[0083] In some example metal-ligand complexes according to Formula (II), R8and R9are independently (Ci-Cio)alkyl. In some specific examples, R8and R9are isopropyl.

[0084] In the metal-ligand complex according to Formulas (I) and (II), each X may be bonded with M through a covalent bond, a dative bond, or an ionic bond. Examples of X as a monodentate ligand include the monodentate ligand being a neutral ligand or a monoanionic ligand. Examples of X as a bidentate ligand include the bidentate ligand being a neutral ligand, a monoanionic ligand, or a dianionic ligand. Monoanionic ligands have a net formal oxidation state of -1. Dianionic ligands have a net formal oxidation state of -2.

[0085] Examples of X as a neutral ligand include the neutral ligand being a neutral Lewis base group such as RJNRKRL, RKORL, RKSRL, or RJPRKRL, where each RJis independently hydrogen, [(Ci-Cio)hydrocarbyl]3Si(Ci-Cio)hydrocarbyl, (Ci-C2o)hydrocarbyl, [(Ci-Cio)hydrocarbyl]3Si, or86409-WO-PCT / DOW 86409 WO18(Ci-C2o)heterohydrocarbyl and each RKand RLis independently hydrogen, (Ci-C2o)hydrocarbyl, or (Ci-C2o)heterohydrocarbyl.

[0086] Examples of X as a monoanionic ligand include the monoanionic ligand being selected from hydride, (Ci-C2o)hydrocarbyl carbanion, (Ci-C2o)heterohydrocarbyl carbanion, halide, nitrate, carbonate, phosphate, sulfate, HC(O)O, HC(O)N(H), (Ci-C2o)hydrocarbylC(0)0~, (Ci-C2o)hydrocarbylC(0)N((Ci-C2o)hydrocarbyl)-, (Ci-C2o)hydrocarbylC(0)N(H), RKRLB, RKRLN, RKO, RKS, RKRLP, or RMRKRLSi, where each RK, RL, and RMis independently hydrogen, (Ci-C2o)hydrocarbyl, or (Ci-C2o)heterohydrocarbyl, or RKand RLare taken together to form a (C2-C2o)hydrocarbylene or (Ci-C2o)heterohydrocarbylene and RMis hydrogen, (Ci-C2o)hydrocarbyl, or (Ci-C2o)heterohydrocarbyl.

[0087] Examples of X as a dianionic ligand include the dianionic ligand being carbonate, oxalate (i.e., −O2CC(O)O−, (C2-C4o)hydrocarbylene dicarbanion, (Ci-C4o)heterohydrocarbylene dicarbanion, phosphate, or sulfate.

[0088] In some example metal-ligand complexes according to Formulas (I) or (II), each X is independently selected from the group consisting of (Ci-Cio)alkyl, (Ce-C2o)aryl, -(CH2)wSi(Rx)3, and halogen. In some examples, each X is independently selected from the group consisting of methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro. In some specific examples, each X is benzyl. In some examples, each X is the same. In some examples, n is 2 and the two X ligands are different from one another.

[0089] In some examples of the supported catalyst systems described herein, the metal-ligand complex is selected from the group consisting of IMLC-1 through IMLC-3:IMLC-1 IMLC-2 IMLC-386409-WO-PCT / DOW 86409 WO19

[0090] In some specific examples, the metal-ligand complex of the supported catalyst systems described herein is IMLC-2 or IMLC-3.Activator Component

[0091] As described above, the supported catalyst systems of the present disclosure include a support, an activator, and a metal-ligand complex having a structure according to Formula (I). The activator of the supported catalyst systems described herein may include any combination of reagents that increases the rate at which a metal-ligand complex oligomerizes or polymerizes unsaturated monomers, such as olefins. The activator may also affect the molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer.

[0092] For example, the metal-ligand complex according to Formula (I) may be rendered catalytically active by contacting the metal-ligand complex to, or combining the metal-ligand complex with, one or more activators. Additionally, the metal-ligand complex according to Formula (I) may include both a procatalyst form, which is neutral, and a catalytic form, which may be positively charged due to the loss of a ligand, such as a benzyl ligand or a phenyl ligand. Suitable activators for use herein include, without limitation: alkyl aluminums; boron-based Bronsted or Lewis acids; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions); and combinations thereof. A suitable activating technique is bulk electrolysis. Combinations of one or more of the foregoing activators and techniques are also contemplated. The term “alkyl aluminum” means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum. Aluminum alkyl or organoaluminum compounds that may be utilized as activators (or scavengers) including trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like.

[0093] Aluminoxane activators may be utilized as an activator for one or more of the metal-ligand complexes described herein. Alumoxane(s) or aluminoxane(s) are generally oligomeric compounds containing -A1(R)-O- subunits, where R is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide. Mixtures of different alumoxanes and modified alumoxanes may also be used. For further descriptions, see U. S. Patent Nos. 4,665,208;86409-WO-PCT / DOW 86409 WO204,952,540; 5,041,584; 5,091,352; 5,206,199; 5,204,419; 4,874,734; 4,924,018; 4,908,463; 4,968,827; 5,329,032; 5,248,801; 5,235,081; 5,157,137; 5,103,031; and EP 0 561 476; EP 0 279 586; EP 0 516 476; EP 0594218; and WO 94 / 10180. In some examples, the activator comprises methylalumoxane (MAO), such as solid methylalumoxane (SMAO).

[0094] In examples, the molar ratio of metal in the activator to metal in the metal-ligand complex is from 0.5:1 to 3500:1, such as from 0.5:1 to 1:1, from 1:1 to 5:1, from 5:1 to 10:1, from 10:1 to 20:1, from 20:1 to 50:1, from 50:1 to 100:1, from 100:1 to 250:1, from 250:1 to 500:1, from 500:1 to 1000:1, from 1000:1 to 1500:1, from 1500:1 to 2000:1, from 2000:1 to 2500:1, from 2500:1 to 3000:1, from 3000:1 to 3500:1, or any combination of two or more of these ranges.

[0095] Lewis acid activators include Group 13 metal compounds containing (Ci-C2o)hydrocarbyl substituents as described herein. In some examples, Group 13 metal compounds are tri((Ci— C2o)hydrocarbyl)-substituted-aluminum or tri((Ci-C2o)hydrocarbyl)-boron compounds. In other examples, Group 13 metal compounds are tri(hydrocarbyl)-substituted-aluminum, tri((Ci— C2o)hydrocarbyl)-boron compounds, tri((Ci-Cio)alkyl)aluminum, tri((C6-Ci8)aryl)boron compounds, and halogenated (including perhalogenated) derivatives thereof. In further embodiments, Group 13 metal compounds are tris(fluoro-substituted phenyl)boranes, tris(pentafluorophenyl)borane. In some examples, the activator is a tris((Ci-C2o)hydrocarbyl borate (e.g. trityl tetrafluoroborate) or a tri((Ci-C2o)hydrocarbyl)ammonium tetra((Ci-C2o)hydrocarbyl)borane (e.g. bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term “ammonium” means a nitrogen cation that is a ((Ci-C2o)hydrocarbyl)4N+a ((Ci-C2o)hydrocarbyl)3N(H)+, a ((Ci-C2o)hydrocarbyl)2N(H)2+, (Ci-C2o)hydrocarbylN(H)3+, or N(H)4+, wherein each (Ci-C2o)hydrocarbyl, when two or more are present, may be the same or different.

[0096] Combinations of neutral Lewis acid activators include mixtures comprising a combination of a tri((Ci-C4)alkyl)aluminum and a halogenated tri((C6-Ci8)aryl)boron compound, especially a tris(pentafluorophenyl)borane. Other examples include combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane. Ratios of numbers of moles of (metal-ligand complex): (tris(pentafluoro-phenylborane): (alumoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluoro-phenylborane): (alumoxane)] are from 1:1:1 to 1:10:30, in other examples, from 1:1:1.5 to 1:5:10.86409-WO-PCT / DOW 86409 WO21

[0097] Exemplary suitable activators include, but are not limited to, methylaluminoxane (MAO), modified methyl aluminoxane (MMAO), triethylaluminum (TEA), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-) amine (RIBS-2), and combinations thereof.

[0098] In particular examples, the activator comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.

[0099] In particular examples, the activator comprises unsubstituted ammonium borate, a monosubstituted ammonium borate, abi-substituted ammonium borate, atri-substituted ammonium borate, or a tetra-substituted ammonium borate.

[0100] In particular examples, the activator comprises bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-) amine (RIBS-2).

[0101] In some examples, more than one of the foregoing activators may be used in combination with each other. A specific example of an activator combination is a mixture of a tri((Ci— C4)hydrocarbyl)aluminum, tri((Ci-C4)hydrocarbyl)borane, or an ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of total number of moles of one or more metal-ligand complexes of Formula (I) to total number of moles of one or more of the activators may be from 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5,000, in some other embodiments, at least 1: 1,000; and 10:1 or less, and in some other embodiments, 1:1 or less. When an alumoxane alone is used as the activator, preferably the number of moles of the alumoxane that are employed is at least 100 times the number of moles of the metal-ligand complex of Formula (I). When tris(pentafluorophenyl)borane alone is used as the activator, in some other embodiments, the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of one or more metal-ligand complexes of Formula (I) from 0.5: 1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activators are generally employed in approximately mole quantities equal to the total mole quantities of one or more metal-ligand complexes of Formula (I).

[0102] In some examples, the supported catalyst systems of the present disclosure may include a scavenger that reacts with any water or other impurities present in the system that might otherwise react with the catalyst leading to reduced efficiency. In embodiments, the supported catalyst systems described herein may include an activator or both an activator and a scavenger.

[0103] In some examples, the activator comprises unsubstituted ammonium borate, a monosubstituted ammonium borate, abi-substituted ammonium borate, atri-substituted ammonium borate,86409-WO-PCT / DOW 86409 WO22or a tetra-substituted ammonium borate, and a scavenger comprising methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.

[0104] In some examples, the activator comprises bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-) amine (RIBS-2), and a scavenger comprising methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.Support Component

[0105] As described above, the supported catalyst systems of the present disclosure include a support, an activator, and a metal-ligand complex having a structure according to Formula (I). The metal-ligand complexes described herein, the activator, or both, may be disposed on the support, which may include one or more support materials. For example, the metal-ligand complexes may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more support materials. The metal-ligand complexes, the activator, or both, may be combined with one or more support materials using one of the support methods well known in the art or as described below. As used in the present disclosure, the metal-ligand complexes, the activator, or both, may be in a supported form, for example, when deposited on, contacted with, or incorporated within, adsorbed or absorbed in, or on, one or more support materials.

[0106] In some embodiments the activator and the support material are contacted together in an inert hydrocarbon liquid to give a suspension of a supported activator in the inert hydrocarbon liquid, then the suspension is contacted with the metal-ligand complex to give a suspension of the supported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed to give the supported catalyst system.

[0107] The removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may include a step of decanting some of the inert hydrocarbon liquid from the suspension. In some embodiments the decanting method comprises pouring off excess inert hydrocarbon liquid from the suspension to give a concentrated suspension of the supported catalyst system.

[0108] The removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may comprise a step of drying the supported catalyst system. The drying step may comprise a spray-drying method.86409-WO-PCT / DOW 86409 WO23

[0109] A “support,” which may also be referred to as a “carrier,” refers to any support material, including a porous support material, such as talc, inorganic oxides, and inorganic chlorides. Other support materials include resinous support materials, e.g., polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.

[0110] Suitable support materials, such as inorganic oxides, include oxides of metals of Group 2, 3, 4, 5, 13 or 14 of the IUPAC periodic table. In embodiments, support materials include silica, which may or may not be dehydrated, fumed silica, alumina (e.g., as described in International Patent Application No. 1999 / 060033), silica-alumina, and mixtures of these. The fumed silica may be hydrophilic (untreated), alternatively hydrophobic (treated). In embodiments, the support material is hydrophobic fumed silica, which may be prepared by treating an untreated fumed silica with a treating agent, such as dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane. In some embodiments, support materials include magnesia, titania, zirconia, magnesium chloride (e.g, as described in U. S. Patent No. 5,965,477), montmorillonite (e.g, as described in European Patent No. 0 511 665), phyllosilicate, zeolites, talc, clays (e.g, as described in U. S. Patent No. 6,034,187), and mixtures of these. In other embodiments, combinations of these support materials may be used, such as, for example, silica-chromium, silica-alumina, silica-titania, and combinations of these.

[0111] Additional support materials may also include those porous acrylic polymers described in European Patent No. 0767 184. Other support materials may also include nanocomposites described in International Patent Application No. 1999 / 047598; aerogels described in International Patent Application No. 1999 / 048605; spherulites described in U. S. Patent No. 5,972,510; and polymeric beads described in International Patent Application No. 1999 / 050311. An example of a support material is fumed silica available under the trade name CABOSIL TS- 610, or other TS- or TG-series supports, available from Cabot Corporation. Fumed silica is typically a silica with particles 7 to 30 nanometers in size that have been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped.

[0112] In embodiments, the support material has a surface area of from 10 square meters per gram (m2 / g) to 700 m2 / g, a pore volume of from 0.1 cubic meters per gram (cm3 / g) to 4.0 cm3 / g, and an average particle size of from 5 microns (pm) to 500 pm. In some embodiments, the support material has a surface area of from 50 m2 / g to 500 m2 / g, a pore volume of from 0.5 cm3 / g to 3.5 cm3 / g, and86409-WO-PCT / DOW 86409 WO24an average particle size of from 10 pm to 200 pm. In other embodiments, the support material may have a surface area of from 100 m2 / g to 400 m2 / g, a pore volume from 0.8 cm3 / g to 3.0 cm3 / g, and an average particle size of from 5 pm to 100 pm. The average pore size of the support material is typically from 10 Angstroms (A) to 1,000 A, such as from 50 A to 500 A or from 75 A to 350 A.

[0113] The support material may comprise silica, alternatively amorphous silica (not quartz), alternatively a high surface area amorphous silica, e.g., from 500 to 1000 m² / g. Such silicas are commercially available from several sources including the Davison Chemical Division of W. R. Grace and Company, e.g., Davison 952 and Davison 955 products, and PQ Corporation, e.g., ES70 product. The silica may be in the form of spherical particles, which may be obtained by a spray-drying process. Alternatively, MS3050 product is a silica from PQ Corporation that is not spray-dried. As procured, these silicas are not calcined (i.e., not dehydrated). Silica that is calcined prior to purchase may also be used as the support material.

[0114] In some embodiments the solid support is a hydrophobic fumed silica. The hydrophobic fumed silica is made by contacting an untreated fumed silica, having surfaces containing silicon-bonded hydroxyl groups (Si-OH groups), with a hydrophobing agent, described later. In some embodiments the hydrophobing agent is a silicon-based hydrophobing agent, containing on average per molecule one or more functional groups reactive with a Si-OH group, to give the hydrophobic fumed silica. The silicon-based hydrophobing agent may be selected from (CH₃)₂SiCl₂, a polydimethylsiloxane, hexamethyldisilazane (HMDZ), and a (C₁–C₁₀)alkyl-Si((C₁–C₁₀)alkoxy)₃ (e.g., an octyltrialkoxysilane such as octyltriethoxysilane, i.e., CH3(CH2)? Si(OCH2CH3)3). In some embodiments the silicon-based hydrophobing agent is dimethyldichlorosilane, i.e., (CH₃)₂SiCl₂. In some embodiments the support material is a dimethyldichlorosilane-treated fumed silica, such as that sold as product TS-610 from Cabot Corporation.

[0115] The support material may be uncalcined or calcined. The calcined support material is made prior to being contacted with a metal-ligand complex, co-catalyst component, and / or hydrophobing agent, by heating the support material in air to give a calcined support material. The calcining comprises heating the support material at a peak temperature from 350 °C to 850 °C, alternatively from 400 °C to 800 °C, alternatively from 400 °C to 700 °C, alternatively from 500 °C to 650 °C and for a time period from 2 to 24 hours, alternatively from 4 to 16 hours, alternatively from 8 to 12 hours, alternatively from 1 to 4 hours, thereby making the calcined support material. If the support material has not been heated in this way it is an uncalcined support material.86409-WO-PCT / DOW 86409 WO25

[0116] In some examples, the ratio of total number of moles of one or more metal-ligand complexes of Formula (I) to the total weight of the support material, e.g., SMAO, may be from 1 pmol / g to 100 pmol / g, from 5 pmol / g to 100 pmol / g, from 10 pmol / g to 100 pmol / g, from 10 µmol / g to 80 µmol / g, from 20 pmol / g to 80 pmol / g, from 20 pmol / g to 60 pmol / g, from 30 pmol / g to 60 pmol / g, from 30 pmol / g to 55 pmol / g, from 35 pmol / g to 55 pmol / g, from 35 pmol / g to 50 pmol / g, or from 40 pmol / g to 50 pmol / g.Polymerization Processes

[0117] As noted above, embodiments of this disclosure are also directed to methods of making an ethylene-based polymer. The methods may include polymerizing, via gas-phase polymerization or slurry-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of a supported catalyst system described herein comprising a metal-ligand complex according to Formula (I). Exemplary polymerization processes may be performed using one or more conventional reactors such as loop reactors, isothermal reactors, fluidized bed reactors, stirred tank reactors, batch reactors in parallel or series, or any combinations thereof.

[0118] In some examples, the method of making an ethylene-based polymer comprises polymerizing, via slurry-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of a supported catalyst system described herein comprising a metal-ligand complex according to Formula (I).

[0119] In some examples, the method of making an ethylene-based polymer comprises polymerizing, via gas-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of a supported catalyst system described herein comprising a metal-ligand complex according to Formula (I).

[0120] In some examples, the method comprises polymerizing the combination of ethylene monomer and at least one 1 -alkene comonomer. In some exemplary methods, the at least one 1 -alkene comonomer comprises 1 -hexene.

[0121] In some exemplary methods of the present disclosure, ethylene monomer, one or more solvents, a supported catalyst system of the present disclosure, and optionally one or more comonomers are fed continuously to the one or more reactors. Exemplary solvents for use as the inert hydrocarbon liquid include, but are not limited to, isobutane, isopentane, pentane, hexane, hexanes,86409-WO-PCT / DOW 86409 WO26heptane, octane, petroleum ether, methylcyclohexane and isoparaffins. For example, such isoparaffin solvents are commercially available under the name ISOPAR E from ExxonMobil Chemical Co., Houston, Texas. When slurry-polymerization is used, the residence time in slurry phase polymerization process can be in the range of from 2 to 180 minutes; for example, from 10 to 60 minutes. The resultant mixture of the ethylene based polymer and solvent is then removed from the reactor and the ethylene based polymer is isolated. Solvent is typically recovered via a solvent recovery unit, i.e. heat exchangers and vapor liquid separator drum, and is then recycled back into the polymerization system.

[0122] In some exemplary methods, the polymerizing is performed at a polymerization temperature less than or equal to the melting or “sintering” temperature of the polymer product. For example, the polymerizing may be performed at a polymerization temperature less than or equal to 130 °C, less than or equal to 125 °C, less than or equal to 120 °C, less than or equal to 115 °C, less than or equal to 110 °C, less than or equal to 105 °C, or less than or equal to 100 °C.

[0123] As discussed above, the supported catalysts systems described herein are able to achieve a combination of lower comonomer incorporation, high weight-average molecular weight Mw, and similar-to-higher activity at lower reactor temperatures, which will allow for the production of polymers with improved product performance in linear low-to-high density polyethylene applications as well as additional process flexibility in the production of poly(ethylene-co-l -alkene) copolymers. Moreover, the high activity at lower reactor temperatures exhibited by the supported catalyst systems described herein is expected to be particularly advantageous in some gas-phase polymerization processes.

[0124] In some examples, the polymerizing may be performed at a polymerization temperature greater than or equal to 30 °C and less than or equal to 130 °C, greater than or equal to 40 °C and less than or equal to 130 °C, greater than or equal to 50 °C and less than or equal to 130 °C, greater than or equal to 60 °C and less than or equal to 130 °C, greater than or equal to 60 °C and less than or equal to 120 °C, greater than or equal to 65 °C and less than or equal to 120 °C, greater than or equal to 65 °C and less than or equal to 115 °C, greater than or equal to 70 °C and less than or equal to 115 °C, greater than or equal to 70 °C and less than or equal to 110 °C, greater than or equal to 75 °C and less than or equal to 110 °C, greater than or equal to 75 °C and less than or equal to 105 °C, greater than or equal to 80 °C and less than or equal to 105 °C, or greater than or equal to 80 °C and less than or equal to 100 °C.86409-WO-PCT / DOW 86409 WO27

[0125] In examples, the concentration of supported catalyst system suspended in an inert hydrocarbon liquid in the slurry-phase polymerization reactor may be up to 50 wt% (weight percent), based on the total weight of the reactor contents,. In some examples, the concentration of supported catalyst system in the slurry-phase polymerization reactor, based on the total weight of the reactor contents, may be up to 40 wt%, up to 30 wt%, up to 20 wt%, up to 10 wt%, up to 5 %, up to 1 %, from 0 to 0.001 wt%, from 0.001 to 0.01 wt%, from 0.01 to 0.1 wt%, from 0.1 to 50 wt%, from 0.1 to 1 wt%, from 1 wt% to 5 wt%, from 5 wt% to 10 wt%, from 10 wt% to 20 wt%, from 20 wt% to 30 wt%, from 30 wt% to 40 wt%, from 40 wt% to 50 wt%, or any combination of two or more of these ranges of solid supported catalyst suspended in the inert hydrocarbon liquid.

[0126] In examples, gases may be used to pressurize the polymerization reactor to a pressure of from 690 kPa (100 psig) to 6,896 kPa (1,000 psig). For example, the reactor pressure of the slurryphase polymerization reactor may be from 690 kPa (100 psig) to 1,379 kPa (200 psig), from 1,379 kPa (200 psig) to 2068 kPa (300 psig), from 2068 kPa (300 psig) to 2,759 kPa (400 psig), from 2,759 kPa (400 psig) to 3,448 kPa (500 psig), or any combination of two or more of these ranges.

[0127] In examples, ethylene monomer may be one of the gases used to pressurize the polymerization reactor. In embodiments, the ethylene partial pressure may be up to 2413 kPa (350 psig), such as from 35 kPa (5 psig) to 137 kPa (20 psig), from 137 kPa (20 psig) to 345 kPa (50 psig), from 345 kPa (50 psig) to 689 kPa (100 psig), from 689 kPa (100 psig) to 1034 kPa (150 psig), from 1034 kPa (150 psig) to 1378 kPa (200 psig), from 1378 kPa (200 psig) to 1723 kPa (250 psig), from 1723 kPa (250 psig) to 2068 kPa (300 psig), from 2068 kPa (300 psig) to 2413 kPa (350 psig), or any combination of two or more of these ranges.

[0128] In some examples, molecular hydrogen gas (H₂) may be used in during polymerization to control the final properties of the ethylene-based polymer. The amount of hydrogen used during polymerization may be expressed as a mole ratio relative to the total polymerizable monomer, such as, for example, ethylene or a blend of ethylene and 1 -hexene. The amount of hydrogen used in the polymerization process may be controlled to achieve desired attributes of the ethylene-based polymer, such as, for example, the weight-average molecular weight of the ethylene-based polymer. In embodiments, the mole ratio of hydrogen to total polymerizable monomer (H₂:monomer) is greater than or equal to 0.0001. For example, the mole ratio of hydrogen to total polymerizable monomer (H2:monomer) may be from 0.0001 to 1.8, from 0.0001 to 1.0, from 0.0001 to 0.10, from 0.0001 to86409-WO-PCT / DOW 86409 WO280.01, from 0.0001 to 0.005, from 0.0001 to 0.002, from 0.0005 to 1.8, from 0.0005 to 1.0, from 0.0005 to 0.10, from 0.0005 to 0.01, from 0.0005 to 0.005, or from 0.0005 to 0.002.

[0129] The amount of hydrogen in the polymerization may also be expressed as a mole ratio relative to the molar amount of ethylene monomer. For example, the mole ratio of hydrogen to total ethylene monomer (H₂: C₂, or H₂ / C₂) may be from 0.0001 to 1.8, from 0.0001 to 1.0, from 0.0001 to 0.10, from 0.0001 to 0.001, from 0.0001 to 0.0005, from 0.0005 to 1.8, from 0.0005 to 1.0, from 0.0005 to 0.10, from 0.0005 to 0.001, from 0.001 to 1.8, from 0.001 to 1.0, from 0.001 to 0.10, from 0.001 to 0.05, from 0.001 to 0.005, or from 0.001 to 0.003.

[0130] In some examples wherein at least one 1 -alkene comonomer is used during polymerization, the ratio between the at least one 1 -alkene comonomer to the ethylene monomer in the polymerization reactor may be from 0.001 to 3, from 0.001 to 2.5, from 0.001 to 2.0, from 0.01 to 2.0, from 0.1 to 2.0, from 0.1 to 1.5, from 0.2 to 1.2, from 0.2 to 1.0, from 0.2 to 0.8, or from 0.4 to 0.8.Polyolefins

[0131] The supported catalyst systems described in the preceding paragraphs are utilized in the polymerization of olefin-based polymers. While the supported catalyst systems of this disclosure are utilized in the polymerization of ethylene, it should be understood that such supported catalyst systems may be utilized in the polymerization of other olefins, such as propylene. In some embodiments, there is only a single type of olefin or 1 -alkene (a-olefin) in the polymerization scheme, creating a homopolymer. However, additional a-olefms may be incorporated into the polymerization procedure. The additional a-olefin comonomers typically have no more than 20 carbon atoms. For example, the additional a-olefin comonomers may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary additional a-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, additional a-olefin comonomers may be selected from the group consisting of propylene, 1 -butene, 1 -hexene, and 1 -octene; or in the alternative, from the group consisting of 1 -hexene and 1 -octene. In some examples, the additional a-alkene comonomer is 1 -hexene.

[0132] The ethylene-based polymers, for example homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as a-olefms, may comprise from at least 50 percent by weight monomer units derived from ethylene, based on a total weight of the ethylene-based polymer. All individual values and subranges encompassed by “from86409-WO-PCT / DOW 86409 WO29at least 50 weight percent” are disclosed herein as separate embodiments; for example, the ethylenebased polymers, homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as ot-olefins may comprise at least 60 weight percent monomer units derived from ethylene; at least 70 weight percent monomer units derived from ethylene; at least 80 weight percent monomer units derived from ethylene; or from 50 to 100 weight percent monomer units derived from ethylene; or from 80 to 100 weight percent units derived from ethylene. Common forms of ethylene-based polymer known in the art include: Low Density Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-site catalyzed Linear Low Density Polyethylene, including both linear and substantially linear low density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).

[0133] In some examples, a poly(ethylene-co-l -alkene) copolymer polymerized in the presence of a supported catalyst system described herein comprises units derived from the ethylene monomer making up at least 50 wt% of the poly(ethylene-co-l -alkene) copolymer, based on a total weight of the poly(ethylene-co-l -alkene) copolymer. For example, the poly(ethylene-co-l -alkene) copolymer may comprise units derived from the ethylene monomer making up at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt% at least 90 wt%, at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, at least 99 wt%, at least 99.5 wt%, at least 99.8 wt%, or at least 99.9 wt% of the poly(ethylene-co-l -alkene) copolymer, based on a total weight of the poly(ethylene-co-l -alkene) copolymer. In some examples, the poly(ethylene-co-l -alkene) copolymer may comprise units derived from the ethylene monomer making up from 50 to 99.99 wt%, from 60 to 99.99 wt%, from 70 to 99.99 wt%, from 80 to 99.99 wt%, from 90 to 99.99 wt%, from 95 to 99.99 wt%, from 96 to 99.99 wt%, from 97 to 99.99 wt%, from 98 to 99.99 wt%, from 99 to 99.99 wt%, from 99 to 99.99 wt%, or from 99.8 to 99.99 wt% of the poly(ethylene-co-l -alkene) copolymer, based on a total weight of the poly(ethylene-co-l -alkene) copolymer.

[0134] In some examples, the poly(ethylene-co-l -alkene) copolymer comprises units derived from the at least one 1 -alkene comonomer making up less than or equal to 10 wt%, less than or equal to 5 wt%, less than or equal to 4 wt%, less than or equal to 3 wt%, less than or equal to 2 wt%, less than or equal to 1 wt%, less than or equal to 0.5 wt%, less than or equal to 0.4 wt%, less than or equal to 0.3 wt%, less than or equal to 0.2 wt%, or less than or equal to 0.1 wt% of the poly(ethylene-co-1 -alkene) copolymer, based on a total weight of the poly(ethylene-co-l -alkene) copolymer. For example, the poly(ethylene-co-l -alkene) copolymer comprises units derived from the at least one86409-WO-PCT / DOW 86409 WO301 -alkene comonomer making up from 0.01 wt% to 10 wt%, from 0.01 wt% to 5 wt%, from 0.01 wt% to 4 wt%, from 0.01 wt% to 3 wt%, from 0.01 wt% to 2 wt%, from 0.01 wt% to 1 wt%, from 0.01 wt% to 0.5 wt%, from 0.01 wt% to 0.4 wt%, from 0.01 wt% to 0.3 wt%, from 0.01 wt% to 0.2 wt%, or from 0.01 wt% to 0.1 wt% of the poly(ethylene-co-l -alkene) copolymer, based on a total weight of the poly(ethylene-co-l -alkene) copolymer.

[0135] In some embodiments, the ethylene-based polymers polymerized in the presence of a supported catalyst system described herein may have a weight-average molecular weight of greater than or equal to 100,000 g / mol, greater than or equal to 200,000 g / mol, greater than or equal to 300,000 g / mol, greater than or equal to 400,000 g / mol, greater than or equal to 500,000 g / mol, greater than or equal to 600,000 g / mol, greater than or equal to 700,000 g / mol, greater than or equal to 800,000 g / mol, greater than or equal to 900,000 g / mol, greater than or equal to 1,000,000 g / mol, greater than or equal to 1,100,000 g / mol, greater than or equal to 1,200,000 g / mol, greater than or equal to 1,300,000 g / mol, greater than or equal to 1,400,000 g / mol, or even greater than or equal to 1,500,000 g / mol. In some examples, the ethylene-based polymers polymerized in the presence of a supported catalyst system described herein may have a weight-average molecular weight of greater than or equal to 100,000 g / mol and less than or equal to 2,000,000 g / mol. In some examples, the ethylene-based polymers polymerized in the presence of a supported catalyst system described herein may have a weight-average molecular weight of greater than or equal to 200,000 g / mol and less than or equal to 2,000,000 g / mol, greater than or equal to 300,000 g / mol and less than or equal to 2,000,000 g / mol, greater than or equal to 400,000 g / mol and less than or equal to 2,000,000 g / mol, greater than or equal to 500,000 g / mol and less than or equal to 2,000,000 g / mol, greater than or equal to 600,000 g / mol and less than or equal to 2,000,000 g / mol, greater than or equal to 700,000 g / mol and less than or equal to 2,000,000 g / mol, greater than or equal to 800,000 g / mol and less than or equal to 2,000,000 g / mol, greater than or equal to 900,000 g / mol and less than or equal to 2,000,000 g / mol, greater than or equal to 1,000,000 g / mol and less than or equal to 2,000,000 g / mol, greater than or equal to 1,100,000 g / mol and less than or equal to 2,000,000 g / mol, greater than or equal to 1,200,000 g / mol and less than or equal to 2,000,000 g / mol, greater than or equal to 1,300,000 g / mol and less than or equal to 2,000,000 g / mol, greater than or equal to 1,400,000 g / mol and less than or equal to 2,000,000 g / mol, or even greater than or equal to 1,500,000 g / mol and less than or equal to 2,000,000 g / mol.

[0136] In some embodiments, the ethylene-based polymers polymerized in the presence of a supported system described herein may have a polydispersity index (PDI) from 1 to 200, where PDI86409-WO-PCT / DOW 86409 WO31is defined as Mw / Mnwith Mwbeing a weight-average molecular weight and Mnbeing a number-average molecular weight. In some examples, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI from 1 to 120, from 1 to 50, from 5 to 50, from 7 to 50, from 7 to 30, from 10 to 50, from 10 to 40, or from 10 to 30.

[0137] The ethylene-based polymers may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymers may contain any amounts of additives. The ethylene-based polymers may compromise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the ethylene-based polymers and the one or more additives. The ethylene-based polymers may further comprise fdlers, which may include, but are not limited to, organic or inorganic fdlers. The ethylene-based polymers may contain from about 0 to about 20 weight percent fdlers such as, for example, calcium carbonate, talc, or Mg(OH)?, based on the combined weight of the ethylene-based polymers and all additives or fdlers. The ethylene-based polymers may further be blended with one or more polymers to form a blend.

[0138] Embodiments of the supported catalyst systems described in this disclosure have the ability to achieve advantageous catalyst activity in combination with tunable polymer properties as will be shown by the examples that follow.Measurement StandardsSymRAD HT-Compositional GPC Analysis

[0139] Mw, Mn, Polydispersity Index (Mw / Mn), and Mzare determined via high-temperature GPC analysis using a Dow Robot Assisted Delivery (RAD) system equipped with a PolymerChar infrared detector (IR5) and Agilent PLgel Mixed A columns.

[0140] Decane (10 pL) is added to each sample for use as an internal flow marker. Samples are first diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm of butylated hydroxytoluene (BHT) to a concentration of 10 mg / mL and dissolved by stirring at 160 °C for 120 minutes. Prior to injection, samples are further diluted with TCB stabilized with BHT to a concentration of 2 mg / mL. Samples (250 pL) are eluted through one PL-gel 20 pm (50 x 7.5 mm) guard column followed by two PL-gel 20 pm (300 x 7.5 mm) Mixed-A columns maintained at 160 °C with TCB stabilized with BHT at a flowrate of 1.0 mL / min. The total run time is 24 minutes. To calibrate for molecular weight86409-WO-PCT / DOW 86409 WO32Agilent EasiCal polystyrene standards (PS-1 and PS-2) are analyzed to create a 3rdorder MW calibration curve. Molecular weight units are converted from polystyrene (PS) to polyethylene (PE) using a daily Q-factor calculated around 0.4 using the average of 5 Dow 38-4 reference samples of known MW. Hexene incorporation is determined using a linear calibration developed by analyzing ethylene-hexene samples with known compositions.

[0141] One or more features of the present disclosure are illustrated in view of the examples as follows:EXAMPLES

[0142] All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexanes, tetrahydrofuran, and diethyl ether were purified via passage through activated alumina and, in some cases, Q-5 reactant. Solvents used for experiments performed in a nitrogen- filled glovebox were further dried by storage over activated 3 A molecular sieves. Glassware for moisture-sensitive reactions was dried in an oven overnight prior to use. NMR spectra were recorded on Bruker Avance NEO 500 or Bruker Avance 400 spectrometers. LC-MS analyses were performed using a Waters e2695 Separations Module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separations were performed on an XBridge C18 3.5 pm 2.1x50 mm column using a 5:95 to 100:0 acetonitrile to water gradient with 0.1% formic acid as the ionizing agent. HRMS analyses were performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8µm 2.1x50 mm column coupled with an Agilent 6230 TOF Mass Spectrometer with electrospray ionization.

[0143] 1H NMR data are reported as follows: chemical shift (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, hept = heptet and m = multiplet), integration, and assignment). Chemical shifts for1H NMR data are reported in ppm downfield from internal tetramethylsilane (TMS, 8 scale) using residual protons in the deuterated solvent as references.13C NMR data were determined with1H decoupling, and the chemical shifts are reported downfield from tetramethylsilane (TMS, 8 scale) in ppm versus the using residual carbons in the deuterated solvent as references.31P NMR chemical shifts were referenced externally to 85 % phosphoric acid (0 ppm).

[0144] Examples 1 to 16 are synthetic procedures for ligand intermediates, ligands, monoanionic spectator ligands, heteroleptic metal precursors, inventive metal–ligand complexes (IMLCs), and comparative metal–ligand complexes (CMLCs). Example 17 describes the experimental procedure86409-WO-PCT / DOW 86409 WO33used to synthesize supported catalysts. In Example 18, the results of Slurry PPR Experiments are tabulated and discussed.Synthesis of Precursor Compounds for 4-Amino-Benzimidazole LigandsExample 13-bromo-N-(4-butylphenyl)-2-nitroanilineDMSO130 °C / 15 h

[0145] A 100 mL round bottom flask was charged with l-bromo-3-fluoro-2-nitrobenzene (12.15 g, 55.23 mmol, 1 equiv), 4-butylaniline (8.722 mL, 55.23 mmol, 1 equiv), and DMSO (50 mL). The mixture was heated to 130 °C for 15 h. After the reaction, DMSO was distilled off and the crude product was purified by column chromatography (Hex: EtOAc 80:20). Yield: 15.2 g, 78.8 %.

[0146] 'H NMR (400 MHz, CDC13) 5 7.20 (tq, J = 10.6, 3.9 Hz, 4H), 7.13 - 7.06 (m, 3H), 2.64 (q, J = 7.8 Hz, 2H), 1.71 - 1.57 (m, 2H), 1.48 - 1.33 (m, 2H), 0.97 (td, J = 7.3, 2.8 Hz, 3H).

[0147] 13C NMR (101 MHz, CDCI3) 5 141.1, 139.8, 137.0, 132.4, 129.7, 124.7, 124.1, 122.6, 116.1, 103.1, 35.1, 33.7, 22.4, 14.0.Example 23-bromo-N-(4-butylphenyl)benzene-l,2-diamineZn (Powder) 1:1 EtOH:sat NH4CI 0 °C to RT

[0148] A 100 mL round bottom was charged with the 3-bromo-N-(4-butylphenyl)-2-nitroaniline (1.30 g, 3.72 mmol), ethanol (30 mL), and sat. aq. NH4CI (10 mL). The mixture was cooled to 0 °C under nitrogen and then Zn powder (1.22 g, 18.6 mmol) was added in portions. The reaction mixture was then allowed to warm to ambient temperature and continue stirring for 2 h. The reaction was monitored by LC-MS. After stirring for 2 h, EtOAc was added and the mixture filtered through86409-WO-PCT / DOW 86409 WO34Celite, then the organic layer was collected and purified by column chromatography (90:10 Hex: EtOAc). Yield = 1.10 g, 93%.

[0149] 1H NMR (400 MHz, CDC13) 57.27 (dd, J = 8.3, 1.5 Hz, 1H), 7.12 - 7.05 (m, 3H), 6.80 - 6.71 (m, 2H), 6.64 (t, J = 7.9 Hz, 1H), 5.15 (s, 1H), 4.22 (s, 2H), 2.58 (t, J = 7.7 Hz, 2H), 1.68 - 1.54 (m, 2H), 1.50 - 1.31 (m, 2H), 0.97 (t, J = 7.3 Hz, 3H).

[0150] 13C NMR (101 MHz, CDCI3) 5 142.21, 139.62, 134.85, 130.53, 129.29, 128.14, 122.49, 119.10, 116.24, 110.05, 34.86, 33.92, 22.38, 14.02.Example 34-bromo-l-(4-butylphenyl)-2-(o-tolyl)-lH-benzo[d]imidazole1. EtOH 2. I2 / K2CO3CH2CI2

[0151] A 100 mL round bottom flask was charged with the 3-bromo-N1-(4-butylphenyl)benzene-1,2-diamine (2.50 g, 7.83 mmol), o-tolualdehyde (0.90 mL, 7.83 mmol), and EtOH (50 mL, absolute). The mixture was heated to 70 °C for 15 h. All volatiles were removed, then CH₂Cl₂ (50 mL), K2CO3 (2.38 g, 17.2 mmol), and I2 (1.99 g, 7.83 mmol) were added and the mixture was allowed to stir for 3 h at ambient temperature. Water was added to the mixture and the organic layer was collected. The crude product was purified by column chromatography (50:50 Hex: CH2C12 (2nd product). Yield = 2.39 g, 73%.

[0152] 'H NMR (400 MHz, CDCI3) 57.56 (d, J = 7.7 Hz, 1H), 7.37 - 7.26 (m, 3H), 7.23 - 7.07 (m, 7H), 2.67 - 2.59 (m, 2H), 2.18 (s, 3H), 1.62 (tt, J = 7.8, 6.4 Hz, 2H), 1.37 (h, J = 7.3 Hz, 2H), 0.95 (t, J = 7.3 Hz, 3H).

[0153] 13C NMR (101 MHz, CDCI3) 5 153.71, 143.32, 141.60, 137.93, 136.33, 133.45, 131.03, 130.22, 129.74, 129.67, 129.43, 126.28, 125.89, 125.41, 124.03, 113.31, 110.00, 35.21, 33.29, 22.34, 20.11, 13.94.86409-WO-PCT / DOW 86409 WO35CM3 Synthesis General Procedure

[0154] The brominated compounds and amines were provided for a Buchwald-Hartwig cross-coupling reaction in a high throughput sequence beginning with a Core-Module 3 (CM3) workflow / procedure.

[0155] Brominated starting materials were reacted with excess amine (2:1). All reactants / reagents were delivered in solution (toluene) with the exception of sodium t-butoxide and the catalyst (weighed as solids). Reactions were diluted with additional reaction solvent to ~10 mL before overnight reaction. The following day reaction conversion was checked via UPLC. After 16 h at 95 °C, conversion was high enough to proceed with purification. Purification consisted of three phases: liquid / liquid extraction, filtration through a plug of silica gel, and then Supercritical Fluid Chromatography (SFC). After removal from the glove box, 5 mL of chloroform and 5 mL of saturated aqueous sodium chloride were added to the reaction vial. The vial was capped, shaken, quickly vented, and then poured off into a 25 mL Biotage ISOLUTE® Phase separator column. An additional 5 mL of chloroform was added, and the organic phase was collected after gravity filtration. The collected material was poured into a GL Sciences 20 mL InertSep PS-SL filter and gravity filtered again. One wash of 5 mL chloroform was similarly used to rinse the phase separation column, then InertSep filter. A final rinse of the silica pad was performed with 5 mL ethyl acetate and the collected samples were concentrated over 10 h at 80 °C under vacuum on a Savant SpeedVac, which ramped at 5 Torr / min. The solids were then subjected to purification using SFC.

[0156] Preparative SFC was carried out using a 1-AA 130 A 5 pm OBD 30 x 150 mm column using CO2 as mobile phase A and 75% acetonitrile:25% isopropanol as mobile phase B. The gradient used was 5% B to 50% B over 10 min with a total flow rate of 100 mL / min. The collection make-up solvent used was ethyl acetate, the BPR pressure was 100 bar, oven temp was 40 °C, the sample concentration was 50 mg / mL and injection volume was 960 pL. The desired compounds were collected by mass spectrometry.86409-WO-PCT / DOW 86409 WO36Synthesis of 4-Amino-Benzimidazole LigandsExample 4Ligand 1 (L-l)nBu

[0157] Ligand 1 was prepared using the CM3 Synthesis General Procedure.

[0158] 'H NMR (400 MHz, CDC13) 5 7.59 (d, J = 8.0 Hz, 1H), 7.38 (d, J = 7.5 Hz, 1H), 7.34 -7.12 (m, 10H), 7.05 (t, J = 7.4 Hz, 1H), 6.92 (d, J = 7.9 Hz, 1H), 6.86 (d, J = 8.1 Hz, 1H), 6.75 (s, 1H), 2.64 (t, J = 7.8 Hz, 2H), 2.41 (s, 3H), 2.23 (s, 3H), 1.63 (qd, J = 8.6, 6.2 Hz, 2H), 1.39 (h, J = 7.3 Hz, 2H), 0.97 (t, J = 7.3 Hz, 3H).

[0159] 13C NMR (101 MHz, CDCI3) 5 150.96, 142.69, 140.25, 137.98, 136.64, 136.39, 134.11, 132.74, 131.05, 131.01, 130.46, 130.44, 130.37, 129.45, 129.24, 126.61, 126.25, 125.54, 124.00, 122.92, 121.15, 104.73, 101.09, 35.22, 33.33, 22.36, 20.16, 18.09, 13.96.Example 5Ligand 2 (L-2)nBu

[0160] Ligand 2 was prepared using the CM3 Synthesis General Procedure.

[0161] 'H NMR (400 MHz, CDCI3) 57.44 - 7.38 (m, 1H), 7.34 - 7.26 (m, 2H), 7.18 (tt, J = 8.4, 4.3 Hz, 10H), 7.04 (t, J = 8.0 Hz, 1H), 6.77 (d, J= 8.1 Hz, 1H), 6.49 (s, 1H), 6.05 (d, J = 7.8 Hz, 1H), 2.69 - 2.58 (m, 2H), 2.35 (s, 6H), 2.22 (s, 3H), 1.68 - 1.56 (m, 2H), 1.38 (dq, J = 14.0, 7.0 Hz, 2H), 0.96 (t,.7= 7.3 Hz, 3H).86409-WO-PCT / DOW 86409 WO37

[0162] 13C NMR (101 MHz, CDCI3) 5 150.62, 142.56, 138.36, 138.00, 137.94, 136.63, 136.21, 134.22, 131.56, 131.09, 130.60, 130.32, 129.37, 129.17, 128.43, 126.25, 125.97, 125.53, 124.18, 102.75, 99.79, 35.21, 33.32, 22.36, 20.11, 18.43, 13.95.Example 6Ligand 3 (L-3)nBu

[0163] Ligand 3 was prepared using the CM3 Synthesis General Procedure.

[0164] 'H NMR (400 MHz, CDC13) 57.46 - 7.40 (m, 1H), 7.40 - 7.26 (m, 4H), 7.21 (s, 2H), 7.01 (t, J = 8.0 Hz, 1H), 6.74 (d,. / = 8.1 Hz, 1H), 6.45 (s, 1H), 6.02 (d, J = 7.8 Hz, 1H), 3.40 (hept, J = 6.8 Hz, 2H), 2.70 - 2.56 (m, 2H), 2.25 (s, 3H), 1.63 (tt, J = 8.0, 6.4 Hz, 2H), 1.45 - 1.33 (m, 2H), 1.21 (d, J= 6.9 Hz, 12H), 0.96 (t, J= 7.3 Hz, 3H).

[0165] 13C NMR (101 MHz, CDCI3) 5 150.48, 148.10, 142.51, 140.24, 137.97, 136.06, 134.97, 134.27, 131.18, 131.09, 130.65, 130.36, 129.35, 129.15, 127.33, 126.25, 125.54, 124.25, 123.78, 102.70, 99.31, 35.21, 33.32, 28.24, 22.36, 20.12, 13.95.Synthesis of Amidine Ligand and Metal PrecursorExample 7N,N-diisopropylbenzimidamideMeMgBrToluener.t., 16 h

[0166] Under a nitrogen atmosphere, diisopropylamine (6.9 mL, 49.4 mmol, 1 equiv) was combined with toluene (77 mL) and heated to 50 °C. A solution of MeMgBr (15.6 mL, 46.9 mmol, 0.95 equiv) was added dropwise and allowed to continue stirring at 50 °C for 1.5 h. The reaction mixture was then cooled to 0 °C and benzonitrile (4.8 mL, 46.4 mmol, 0.95 equiv) was added dropwise. The reaction mixture was allowed to warm to ambient temperature and continue stirring86409-WO-PCT / DOW 86409 WO38for 16 h. The reaction was then cautiously quenched with water (50 mL), causing a separation of the aqueous and organic phases. The aqueous layer was extracted with diethyl ether (2 x 50 mL) and combined with the organic layer. The combined organic layers were then dried over Na2SO4, fdtered, and the solvents were removed under reduced pressure. Vacuum distillation afforded a colorless oil which was then mixed with pentane (20 mL) and dried over CaH₂ for 16 h. Following fdtration and removal of the pentane in vacuo, the product crystallized as a colorless powder. Yield: 6.8 g, 67.3 %.

[0167] 'H NMR (300 MHz; CDC13) 5 7.42 - 7.22 (m, 5H), 5.85 (s, 2H), 2.97 (m, 2H), 1.09 (d, 12H).Example 8(amid-Ph)ZrBn3Bn1 Toluene ZrBn 1 BnBn r.t., 1 h

[0168] In a glovebox, a jar was charged with ZrBn₄ (1 g) and a vial was charged with N, N-diisopropylbenzimidamide (0.448 g). Toluene (5 mL) was added to each. The ligand solution was added dropwise to the zirconium complex solution while vigorously stirring. The mixture was then stirred for 1 h, fdtered, pumped down and triturated with hexanes (20 mL), fdtered and the solid washed with hexanes to afford a yellow solid (0.914 g, 73%) after drying.

[0169] 'H NMR (500 MHz, C6D6) 87.10 (t, J= 7.7 Hz, 6H), 7.06 (d, J = 7.7 Hz, 2H), 7.02 - 6.97 (m, 1H), 6.97 - 6.89 (m, 5H), 6.57 (d, J = 7.7 Hz, 6H), 3.39 (br s, 2H), 1.78 (s, 6H), 1.60 (br s, 6H), 0.68 (br s, 6H).

[0170] 13C NMR (126 MHz, C6D6) 8 161.86, 142.99, 142.79, 130.38, 128.58, 127.65, 127.25, 125.34, 122.36, 63.21, 20.40; note that the iPr methine resonance appears to be broadened into the baseline. Single crystals of the complex were grown from the hexanes washings after storing at -35°C.General Procedure for Metal-Ligand Complex Synthesis

[0171] Inside a nitrogen filled glovebox, a 0.5 to 2 mL aliquot from a 5 mM toluene solution of benzimidazole-amine ligand was transferred to a 7 mL glass vial and the volatiles were removed in vacuo. The mass of the resulting residue was measured and 1 equiv of a 5 mM C6D6 solution of86409-WO-PCT / DOW 86409 WO39amidine metal precursor was added to the vial at ambient temperature. After combining the ligand material and solution of metal precursor, the mixture was transferred to an NMR tube and checked by1H NMR spectroscopy to ensure conversion to the target complex, which was confirmed by the appearance of one equivalent of toluene. After confirmation, the NMR sample was returned to the glovebox and all volatiles were removed. Ligand and metal precursor were in contact at ambient temperature with each other for 2 to 24 h at ambient temperature to ensure product formation. All volatiles were removed under reduced pressure and the crude product was used without further purification for supporting on SDMAO, and then PPR testing.Synthesis of Inventive Metal-Ligand ComplexesExample 9IMLC-1

[0172] Inventive metal-ligand complex IMLC-1 was prepared using the General Procedure for Metal-Ligand Complex Synthesis using Ligand 1 as the 4-amino-benzimidazole ligand and (amid-Ph)ZrBn3 as the metal precursor.

[0173] 'H NMR (500 MHz, C6D6) 87.59 (s, 1H), 7.15 - 6.90 (m, 17H), 6.88 - 6.74 (overlapping resonances, 5H), 6.74 (d, J = 8.1 Hz, 2H), 6.61 - 6.52 (m, 4H), 5.99 (d, J = 7.8 Hz, 1H), 4.11 (br s, 1H), 3.40 (br s, 1H), 2.67 (br s, 1H), 2.57 (br s, 1H), 2.47 (br s, 1H), 2.40 (br s, 1H), 2.20 (t, J = 7.8 Hz, 2H), 2.18 (s, 3H), 2.03 - 1.77 (br s, 3H), 1.26 (m, J = 6.2 Hz, 2H), 1.11 (m,. / = 7.3 Hz, 2H), 0.78 (t, J = 7.3 Hz, 3H). Note: Resonances attributable to the methyls of the amidine ligand isopropyl groups are broadened into the baseline between 8 1.40 - 0.58 (12H).Example 10IMLC-2

[0174] Inventive metal-ligand complex IMLC-2 was prepared using the General Procedure for Metal-Ligand Complex Synthesis using Ligand 2 as the 4-amino-benzimidazole ligand and (amid-Ph)ZrBn3 as the metal precursor.

[0175] 'H NMR (500 MHz, C6D6) 8 7.67 - 7.62 (m, 1H), 7.15 - 6.97 (overlapping resonances, 13H), 6.97 - 6.90 (m, 1H), 6.86 (t, J = 7.4 Hz, 1H), 6.80 (t, J = 7.4 Hz, 1H), 6.78 - 6.75 (m, 4H), 6.74 (d, J= 8.3 Hz, 2H), 6.60 (dd,. / = 8.1, 0.8 Hz, 1H), 6.50 (d, J= 7.6 Hz, 2H), 6.41 (d, J= 7.6 Hz, 2H), 5.94 (dd, J = 7.8, 0.7 Hz, 1H), 4.48 - 4.14 (br s, 1H), 3.55 - 3.18 (br s, 1H), 2.65 (d, J = 9.7 Hz, 1H), 2.62 (d, J = 9.0 Hz, 1H), 2.53 (d, J = 9.7 Hz, 1H), 2.42 (d, J = 9.0 Hz, 1H), 2.23 - 2.18 (m, 2H), 2.12 (s, 3H), 2.09 (s, 3H), 1.96 (s, 3H), 1.26 (m, 2H), 1.11 (m, 2H), 0.78 (t, J= 7.3 Hz, 3H). Note:86409-WO-PCT / DOW 86409 WO40Resonances attributable to the methyls of the amidine ligand isopropyl groups are broadened into the baseline between 8 1.30 - 0.58 (12H).Example 11IMLC-3

[0176] Inventive metal-ligand complex IMLC-3 was prepared using the General Procedure for Metal-Ligand Complex Synthesis using Ligand 3 as the 4-amino-benzimidazole ligand and (amid-Ph)ZrBn3 as the metal precursor.

[0177] 1H NMR (500 MHz, C6D6) δ 7.75 (d, J= 7.1 Hz, 1H), 7.29 - 7.21 (overlapping resonances, 2H), 7.15 - 6.90 (overlapping resonances, 15H), 6.85 - 6.74 (overlapping resonances, 2H), 6.76 -6.70 (overlapping resonances, 2H), 6.64 (d, J = 8.1 Hz, 1H), 6.61 - 6.54 (overlapping resonances, 3H), 6.33 (d, J = 7.7 Hz, 2H), 5.93 (d, J = 7.9 Hz, 1H), 4.51 (br s, 1H), 3.42 (br s, 1H), 3.30 (hept, J = 6.8 Hz, 1H), 3.08 (hept, J = 6.8 Hz, 1H), 2.83 (d, J = 9.7 Hz, 1H), 2.73 (d, J = 9.8 Hz, 1H), 2.57 (d, J = 9.2 Hz, 1H), 2.41 (d, J = 9.3 Hz, 1H), 2.20 (t, J = 7.8 Hz, 2H), 1.99 (s, 3H), 1.30 (d, J = 6.8 Hz, 3H), 1.25 (q, J = 7.7 Hz, 2H), 1.15 - 1.06 (overlapping resonances, 11H), 1.01 (d, J = 6.7 Hz, 3H), 0.97 (d, J = 6.8 Hz, 3H), 0.79 - 0.76 (overlapping resonances, 9H).Synthesis of Comparative Metal-Ligand Complexes (CMLCs)

[0178] The structures of comparative metal-ligand complexes CMLC-2 and CMLC-3 are shown below:CMLC-2 CMLC-386409-WO-PCT / DOW 86409 WO41Example 12CpZrBn3! 3.15 equiv BnMgCICI' i 'CI - ► BnXlXBnCl TolueneBn-25 °C to r.t., 1 h

[0179] In a glovebox, CpZrCl3 (1.15 g, 4.37 mmol, 1 equiv), a magnetic stir bar, and toluene (10 mL) were combined in a 50 mL glass jar and stored at -25 °C for 60 min. Separately, a 1.0 M solution of BnMgCI in diethyl ether (13.78 mL, 13.78 mmol, 3.15 equiv) was added to a 20 mL vial and also stored at -25 °C for 60 min. After this cooling time, the Grignard solution was added dropwise to the gray / brown suspension of Zr precursor in toluene while stirring vigorously. The suspension gradually turned vibrant yellow / orange as the addition was carried out. The reaction mixture was then allowed to warm to room temperature and left to continue stirring vigorously at ambient temperature for 60 min. The resulting bright yellow suspension was then filtered through a disposable filter and the filter cake was washed with toluene (10 mL). The golden yellow filtrate was concentrated under vacuum, affording a bright yellow solid that was triturated with hexanes (2 x 10 mL) and washed with hexanes (2 x 20 mL). The bright yellow solid was then extracted into in toluene (2 x 20 mL) and concentrated to 10 mL prior to storage at -25 °C for 48 h. Yellow crystals were collected by separating the mother liquor and washing the crystals with hexanes (1.5 mL). The crystals were dried under vacuum and stored at -25 °C as a solid. Yield: 1.20 g, 63.9 %. 'H NMR (400 MHz, C6D6) 87.11 - 7.04 (m, 6H), 6.99 - 6.92 (m, 3H), 6.50 - 6.44 (m, 6H), 5.60 (s, 5H), 1.49 (s, 6H).13C NMR (101 MHz, C6D6) 8 143.5, 130.1, 127.6, 123.6, 111.9, 65.7.Example 13CMLC-2

[0180] Comparative metal-ligand complex CMLC-2 was prepared using the General Procedure for Metal-Ligand Complex Synthesis using Ligand 2 as the 4-amino-benzimidazole ligand and CpZrBn3 as the metal precursor.

[0181] 'H NMR (500 MHz, C6D6) 8 7.89 - 7.84 (m, 1H), 7.20 (t, J = 7.6 Hz, 2H), 7.14 - 7.08 (overlapping multiplets, 4H), 7.07 - 7.00 (overlapping multiplets, 4H), 6.99 - 6.95 (overlapping multiplets, 2H), 6.92 - 6.87 (m, 2H), 6.83 (t, J = 7.4 Hz, 2H), 6.69 (d, J = 8.1 Hz, 2H), 6.66 - 6.61 (m, 2H), 6.58 (dd, J = 8.1, 0.7 Hz, 1H), 5.89 (dd, J = 7.9, 0.7 Hz, 1H), 5.68 (s, 5H), 3.08 (d, J = 10.786409-WO-PCT / DOW 86409 WO42Hz, 1H), 2.51 (d,. / = 10.6 Hz, 1H), 2.31 (d, J= 10.7 Hz, 1H), 2.22 -2.15 (m, 3H), 2.14 (s, 3H), 2.09 (s, 3H), 1.85 (s, 3H), 1.28 - 1.18 (m, 2H), 1.14 - 1.04 (m, 2H), 0.76 (t, J = 7.3 Hz, 3H).Example 14Tricyclohexyl-phosphinimine (Cy3PNH)Cy N3SiMe3MeOH NHIIP^Cy Cy Toluene Cy ^Cy Toluene I85 °C, 18 h 40 °C, 12 h Cy

[0182] In a glovebox, tricyclohexylphosphine (0.750, 2.67 mmol, 1 equiv) was added to a 40 mL glass vial along with a magnetic stir bar and toluene (6 mL) at ambient temperature. Trimethylsilyl azide (0.531 mL, 4.01 mmol, 1.5 equiv) was added dropwise at ambient temperature while maintaining gentle stirring. After the addition was complete, the reaction was heated to 85 °C for 18 h. The reaction mixture was cooled to ambient temperature, filtered, and concentrated to dryness. The resulting residue was triturated with hexanes (2 x2 mL) and the volatiles were removed in vacuo, affording a solid. The material was redissolved in toluene (2 mL), and an excess of anhydrous methanol (2 mL) was added. The resulting mixture was stirred for 12 h at 40 °C. The mixture was concentrated to a solid. The solid was triturated with hexanes (3 x 2 mL), washed with hexanes (2 x 2 mL), and dried in vacuo, affording a nearly colorless solid. Yield: 0.61 g, 77.2%. 'H NMR (400 MHz, C6D6) 82.01 - 1.80 (m, 6H), 1.80 - 1.48 (m, 12H), 1.48 - 1.23 (m, 6H), 1.21 - 0.99 (m, 9H), 0.23 (s, 1H).13C NMR (101 MHz, C6D6) 8 128.30, 128.29, 128.06, 128.05, 127.82, 127.81, 36.40, 35.85, 27.51, 27.40, 27.34, 27.23, 27.20, 26.87, 26.72, 26.70.31P NMR (162 MHz, C6D6) 836.57.Example 15Cy3PNZrBn3CyCy Cy^^CyCy^^Cy?nToluene IINHBnBnBnr.t., 18 hBnzI BnBn

[0183] In a glovebox, a vial was charged with ZrBn₄ (0.500 g, 1.097 mmol) and Cy3PNH (0.324 g, 1.097 mmol) and toluene (5 mL). The mixture was stirred overnight, concentrated and triturated with hexanes to afford a pale yellow solid. 'H NMR (400 MHz, C6D6) 5 7.21 - 7.12 (m, 6H), 6.95 (t, J = 7.4 Hz, 3H), 6.83 (d, J = 6.8 Hz, 6H), 1.96 (s, 6H), 1.79 (d, J = 13.6 Hz, 6H), 1.75 - 1.66 (m, 6H), 1.64 - 1.52 (m, 6H), 1.29 (q, J = 12.5 Hz, 6H), 1.09 (d, J = 7.9 Hz, 9H).13C NMR (126 MHz,86409-WO-PCT / DOW 86409 WO43C6D6) 8 144.16, 129.76, 126.66, 121.50, 59.31, 36.04, 35.58, 26.88, 26.78, 26.71, 26.69, 26.14.31P NMR (202 MHz, C6D6) 8 16.62.Example 16CMLC-3

[0184] Comparative metal-ligand complex CMLC-3 was prepared using the General Procedure for Metal-Ligand Complex Synthesis using Ligand 3 as the 4-amino-benzimidazole ligand and Cy3PNZrBn3, as the metal precursor.

[0185] 'H NMR (500 MHz, C6D6) 87.81 (d, J= 7.5 Hz, 1H), 7.34 - 7.20 (overlapping multiplets, 6H), 7.13 - 6.98 (overlapping multiplets, 10H), 6.84 (d, J = 7.6 Hz, 2H), 6.76 - 6.67 (m, 2H), 6.67 -6.58 (m, 2H), 5.99 (d, J = 7.9 Hz, 1H), 3.65 - 3.48 (m, 2H), 3.10 (br s, 1H), 3.00 (br s, 1H), 2.76 (br s, 1H), 2.64 (br s, 1H), 2.19 (t, J = 7.8 Hz, 2H), 1.92 (s, 3H), 1.70 - 1.52 (broad and overlapping, 18H), 1.40 - 1.17 (broad and overlapping, 16H), 1.15 - 1.03 (broad and overlapping, 16H), 0.76 (t, J = 7.2 Hz, 3H).Example 17Synthesis of Supported Catalysts

[0186] In a nitrogen filled continuous purge glovebox, unsupported metal-ligand complexes are diluted to 4.21 mM in anhydrous deoxygenated toluene, and pipetted into oven-dried 4 mL or 8 mL scintillation vials containing a pre-weighed amount of SMAO such that the resultant slurry is 45 umol Zr or Hf per 1 g SMAO, unless otherwise noted. The metal-ligand complex slurries are stirred at 300 rpm and heated to 50 °C for 30 minutes, then returned to ambient temperature. Colorization of the previously white SMAO indicates the catalyst has been supported, but is not quantified or recorded at this stage. 'H-NMR experiments of the remaining liquid reveals no remaining metal-ligand complex or active catalyst present in the liquid layer. Therefore, supporting reactions are assumed to reach full conversion. The room temperature slurries are moved to a vortexing unit and agitated at 700 rpm for uniform dispersion. Slurries are agitated for at least one minute before an aliquot may be daughtered by positive displacement tip (PDT) into an 8 mL vial, and vortexing continues during the daughtering process. Daughters (or supported catalysts) are diluted with Isopar E to 50 - 500 nmol per mL depending on the expected PPR performance. Catalyst materials and supported catalysts are kept in a glovebox freezer at -30 °C for storage.

[0187] Supported inventive metal-ligand complexes S-IMLC-1, S-IMLC-2, and S-IMLC-3 were prepared using the above procedure for synthesizing supported catalysts with IMLC-1, IMLC-2, and86409-WO-PCT / DOW 86409 WO44IMLC-3, respectively, as the metal-ligand complex to be supported. Supported comparative metal-ligand complexes S-CMLC-2 and S-CMLC-3 were prepared using the above procedure for synthesizing supported catalysts with CMLC-2 and CMLC-3, respectively, as the metal-ligand complex to be supported.Example 18Polymerization ReactionsExperimental Procedure for Slurry PPR Experiments

[0188] The 48 PPR-A reactor cells were prepared as follows the prior day before the PPR run. An oven-dried pre-weighed library of glass tubes were manually inserted into the reactor wells, the PEEK stir paddles were attached to the module heads, and the module heads were attached to the module bodies. The reactors were heated to 190 °C, purged with nitrogen for 10 hours, and cooled to 50 °C. On the day of the experiment, the reactors were purged twice with ethylene and vented completely to purge the lines. The reactors were then pre-heated to 50 °C and the stirrers turned on at 800 rpm.

[0189] The reactors were filled to the appropriate solvent level with Isopar-E and the comonomer (1 -hexene) using the robotic needle to give a final total volume of 5 mL (once all of the reagent solutions are added later). The solvent and comonomer injections loading modules 1-3 were performed using the left robotic arm and the solvent injections loading modules 4-6 used the right robotic arm with both arms operating simultaneously. Following solvent injection, the reactors were heated to final desired temperature (80 °C or 100 °C) and stirring increased to programmed set points. When the reactors reached the temperature set point, which required about 10 to 30 minutes depending on the desired temperature, the cells were pressurized to the desired set point with either pure ethylene, or a mixture of ethylene and hydrogen from the gas accumulator, and the solvent saturated (as observed by the gas uptake). If the ethylene-hydrogen mixture was used, once the solvent was saturated in all cells, the gas feed line was switched from the accumulator to pure ethylene for the remainder of the run.

[0190] The robotic synthesis protocol was then initiated whereby the activator slurry (SMAO) was injected first, followed by the supported catalyst slurries. The reagent and chase injections loading modules 1-3 were performed using the left robotic arm and the solvent injections loading modules 4-6 used the right robotic arm with both arms operating simultaneously. Both injections for a given cell were completed before the robot started the injection of the next cell in the sequence.86409-WO-PCT / DOW 86409 WO45Each reagent addition was chased with 500 uL of Isopar-E solvent to ensure the complete injection of the reagent. After each reagent addition, the needles were washed with Isopar-E inside and outside the needle.

[0191] At the moment of the catalyst injection in each individual cell, a reaction timer was started and the PPR software began monitoring the pressure of each cell. The desired pressure (within approximately 2-6 psig) was maintained by the supplemental addition of ethylene gas by opening the valve at the set point minus 2 psi and closing it when the pressure reached 2 psi above set point. All drops in pressure were cumulatively recorded as uptake of the ethylene for the duration of the run. The polymerization reactions proceeded for 90 minutes or to an ethylene uptake of 90 psi, whichever occurred first, and then were quenched by adding a 60 psi overpressure of 10% (v / v) CO2 in argon. Data collection continued for 5 minutes after the quench of each cell. After the last cell finished quenching, any potential leaks identified from the pressure and uptake curves were noted, the reactors were cooled down to 50 °C, vented, and the PPR tubes removed from the module blocks. The PPR library tubes were removed from the drybox and the volatiles were then removed using the Genevac rotary evaporator. Once the library vials were re-weighed to obtain the yields, the library was submitted for high throughput polymer analytical.

[0192] Table 1 presents results of polymerization reactions performed under high density conditions at a polymerization temperature of 100 °C and in accordance with the Experimental Procedure for Slurry PPR Experiments disclosed herein.TABLE 1: Catalyst activity (quench time), Mw, PDI, hexene incorporation Mz, and yield of polymers produced in slurry parallel pressure reactor under high density conditions at 100 °CSupported Loading Uptake Quench Mw Mz Hexene Yield PDICatalyst (nmol) (psi) Time (s) (g / mol) (g / mol) (wt%) (mg) S-IMLC-1 25 90 2,910 1,514,794 7.7 2,979,626 0.1 138 S-IMLC-2 25 90 1,106 1,249,834 17 2,999,013 0 145 S-IMLC-3 25 91 677 1,209,271 10.4 2,575,739 0.1 136S-CMLC-2 25 90 1,344 206,597 14.4 1,637,742 0 113S-CMLC-3 25 90 1,239 89,656 3.4 585,277 3.7 168 ♦Slurry PPR conditions: Temp. = 100 °C, IsoparE = 5 mL, C6 / C2 (molar ratio) = 0.6 in liquid, H2 / C2 (molar ratio) = 0.0016 in liquid, run time = 90 mins max (5400 s), Quench time = time needed to uptake 90 psi of ethylene; the faster the quench time, the more active the catalyst is. All catalysts are 45 µmol Zr / g SMAO; n.d. = not determined.86409-WO-PCT / DOW 86409 WO46

[0193] Table 2 presents results of polymerization reactions performed under high density conditions at a polymerization temperature of 80 °C and in accordance with the Experimental Procedure for Slurry PPR Experiments disclosed herein.TABLE 2: Catalyst activity (quench time), Mw, PDI, hexene incorporation Mz, and yield of polymers produced in slurry parallel pressure reactor under high density conditions at 80 °CSupported Loading Uptake Quench Mw Mz Hexene Yield PDICatalyst (nmol) (psi) Time (s) (g / mol) (g / mol) (wt%) (mg) S-IMLC-2 25 90 898 857,150 11.6 1,836,311 0.1 135 S-IMLC-3 25 90 948 1,360,942 27.5 2,926,829 0.0 118S-CMLC-2 25 90 1,826 146,911 8.7 612,321 0.0 102S-CMLC-3 25 90 1,504 753,663 6.2 2,029,355 0.6 130 ♦Slurry PPR conditions: Temp. = 80 °C, IsoparE = 5 mL, C6 / C2 (molar ratio) = 0.6 in liquid, H2 / C2 (molar ratio) = 0.0016 in liquid, run time = 90 mins max (5400 s), Quench time = time needed to uptake 90 psi of ethylene; the faster the quench time, the more active the catalyst is. All catalysts are 45 µmol Zr / g SMAO; n.d. = not determined.

[0194] The slurry reactor results for the effective SMAO supported catalysts, S-IMLC-1 through S-IMLC-3, made from IMLC-1 through IMLC-3, are shown in Tables 1 and 2 above. High activity is deemed as quench times of 1,500 seconds or faster at catalyst charges of 25 nmol or lower at 45 pmol Zr or Hf / g SMAO or lower. The quench time is the time it takes to consume 90 psi of ethylene during the experiment, where the faster the time, the more active the catalyst. Under process relevant high density conditions at 100 °C (Table 1), the activity for the SMAO-supported catalysts, S-IMLC-2 and S-IMLC-3, are better than those of alternative heteroleptic comparative examples S-CMLC-2 (bearing a cyclopentadienyl ligand) and CMLC-3 (bearing a phosphinimide ligand). Specifically, the inventive examples S-IMLC-2 and S-IMLC-3 have quench times of 677 seconds and 1,106 seconds, respectively, whereas the comparative examples S-CMLC-2 and S-CMLC-3 have quench times of 1,239 seconds and 1,344 seconds, respectively.

[0195] Of the SMAO-supported catalysts that were evaluated at 80 °C (Table 2), S-IMLC-2 and S-IMLC-3 displayed activities better than the relevant heteroleptic comparative examples, S-CMLC-2 and S-CMLC-3. Specifically, the inventive examples S-IMLC-2 and S-IMLC-3 have quench times of 898 seconds and 948 seconds, respectively, compared to the quench times of 1,504 seconds and 1,826 seconds, respectively, for comparative examples S-CMLC-2 and S-CMLC-3. Optimal activity was observed for those metal-ligand complexes of the present disclosure possessing86409-WO-PCT / DOW 86409 WO47two or / Ao-substituents on the A-aryl amine group of the 4-amino-benzimidazole ligand such as, but not limited to, methyl (IMLC-2) and isopropyl (IMLC-3).

[0196] Moreover, based on the GPC analysis of the polyethylene-hexene copolymers produced under these slurry process conditions at 100 °C (Table 1), the inventive supported catalysts produce polyethylene with ultra-high weight-average polymer molecular weight ranging from 1,200,000 g / mol to 1,500,000 g / mol, which is significantly higher than S-CMLC-2 and S-CMLC-2, which produced polymers with weight-average molecular weights ranging from 89,656 g / mol to 206,597 g / mol. The GPC analysis of the polyethylene-hexene copolymers produced by SMAO-supported catalysts evaluated at 80 °C (Table 2) also revealed higher weight-average molecular weights for the inventive heteroleptic 4-amino-benzimidazole amidine complexes. Specifically, while the metal-ligand complex of inventive example S-IMLC-2 has the same 4-amino-benzimidazole ligand as the metal-ligand complex of the comparative example S-CMLC-2, but differs in that it also bears an amidine spectator ligand, unlike the comparative example S-CMLC-2 which bears a cyclopentadienyl spectator ligand, produces a copolymer with a weight-average molecular weight of 857,105 g / mol, which is nearly six times greater than that of S-CMLC-2 (146,911 g / mol). Similarly, while the metal-ligand complex of inventive example S-IMLC-3 has the same 4-amino-benzimidazole ligand as the metal-ligand complex of the comparative example S-CMLC-3, but differs in that it also bears an amidine spectator ligand, unlike the comparative example S-CMLC-2 which bears a phosphinimide spectator ligand, produces a copolymer with a weight-average molecular weight ofl,360,942 g / mol, which is nearly two times greater than that of S-CMLC-3 (753,663 g / mol). The polymers produced by the inventive supported complexes S-IMLC-1 through S-IMLC-3 also have broad molecular weight distributions with poly dispersity indexes often greater than 10 and, in one case, as high as 27.5 (S-IMLC-3 at 80 °C).

[0197] The good activity combined with ultra-high molecular weight capability and broad molecular weight distributions achieved by the supported catalyst systems described herein shows that the supported catalyst systems of the present disclosure may be used to produce resins with potential advantageous properties for both single and multi-catalyst applications. Furthermore, the improved or comparable activity at lower reactor temperatures (80 °C vs 100 °C) demonstrated by these S-IMLCs is an advantage in many gas-phase polyolefin production processes where lower operating temperatures are often required to enhance operability.86409-WO-PCT / DOW 86409 WO48

[0198] It is noted that the terms “substantially” and “about” may be utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. These terms are also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue. The term “substantially” is used herein also to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue. Thus, it is used to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation, referring to an arrangement of elements or features that, while in theory would be expected to exhibit exact correspondence or behavior, may in practice embody something less than exact.

[0199] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. The terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting. As used in the specification and appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0200] It is noted that one or more of the following claims utilize the term “wherein” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”

[0201] It should be understood that where a first component is described as “comprising” or “including” a second component, it is contemplated that, in some embodiments, the first component “consists” or “consists essentially of’ the second component. Additionally, the term “consisting essentially of’ is used in this disclosure to refer to quantitative values that do not materially affect the basic and novel characteristic(s) of the disclosure.

[0202] It should be understood that any two quantitative values assigned to a property or measurement may constitute a range of that property or measurement, and all combinations of ranges formed from all stated quantitative values of a given property or measurement are contemplated in this disclosure.86409-WO-PCT / DOW 86409 WO49

[0203] It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the specification cover the modifications and variations of the various embodiments described herein provided such modification and variations come within the scope of the appended claims and their equivalents.

Claims

86409-WO-PCT / DOW 86409 WO50CLAIMS1. A supported catalyst system comprising a support, an activator, and a metal-ligand complex having a structure according to Formula (I):where:M is a metal selected from the group consisting of titanium, zirconium, and hafnium, the metal having a formal oxidation state of +2, +3, or +4;each X is a monodentate or bidentate ligand independently selected from the group consisting of unsaturated (C2-C3o)hydrocarbon, unsaturated (C2-C3o)heterohydrocarbon, (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, halogen, -N(RX)2, and -(CH2)wSi(Rx)3, where w is 1 to 10 and each Rxis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl;n is 0, 1, or 2;each of R1and R5is independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl;each of R2, R3, R4, and R6is independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H;each of Subi and Sub2 is independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, and (C3-C3o)heteroaryl, -ORC, -N(RC)2, -Si(Rc)3, -Ge(Rc)3, and -H, wherein Subi and86409-WO-PCT / DOW 86409 WO51Sub? are optionally covalently connected to form an aromatic ring, a non-aromatic ring, or a multi-ring structure; andeach Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, and -H.2 The supported catalyst system of claim 1, wherein:M is zirconium or hafnium;each X is independently selected from the group consisting of (Ci-Cio)alkyl, (C6-C?o)aryl, -(CH2)wSi(Rx)3, and halogen; andR1is (Ci-C3o)alkyl or (Ce-C3o)aryl.3 The supported catalyst system of either one of claims 1 or 2, wherein R1is 2-methylphenyl, 2,6-dimethylphenyl, or 2,6-di(iso-propyl)phenyl.4 The supported catalyst system of any one of claims 1 to 3, wherein R6is (C6-C?o)aryl or (C3-C2o)cycloalkyl.5 The supported catalyst system of any one of claims 1 to 4, wherein R6is 2-methylphenyl.6 The supported catalyst system of any one of claims 1 to 5, wherein R5is (Ci-Cio)alkyl or (C6-C2o)aryl.7 The supported catalyst system of any one of claims 1 to 6, wherein R5is 4-butylphenyl.8 The supported catalyst system of any one of claims 1 to 7, wherein R2, R3, and R4are -H.9 The supported catalyst system of any one of claims 1 to 8, wherein the metal-ligand complex has a structure according to Formula (II):86409-WO-PCT / DOW 86409 WO52where:each of R1-6, X, M, and n are defined as in Formula (I); andeach of R7, R8, and R9is independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, and halogen, wherein optionally, any of R7, R8, and R9are covalently connected to form at least one of an aromatic ring, a non-aromatic ring, or a multi-ring structure.

10. The supported catalyst system of claim 9, wherein R7is unsubstituted phenyl.

11. The supported catalyst system of either one of claims 9 or 10, wherein R8and R9are isopropyl.

12. The supported catalyst system of any one of claims 1 to 11, wherein each X is independently selected from the group consisting of methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro.

13. The supported catalyst system of any one of claims 1 to 12, wherein each X is benzyl.86409-WO-PCT / DOW 86409 WO5314. The supported catalyst system of any one of claims 1 to 13, wherein the metal-ligand complex is selected from the group consisting of IMLC-1, IMLC-2, and IMLC-3:IMLC-1 IMLC-2 IMLC-315. A method of making an ethylene-based polymer, the method comprising:polymerizing, via gas-phase polymerization or slurry-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of the supported catalyst system of any one of claims 1

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