Amidine complexes bearing 4-amino-benzimidazole ligands for making poly(ethylene-co-1-alkene)

Abstract

Catalyst systems comprising 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

86637-WO-PCT / DOW 86637 WO1AMIDINE COMPLEXES BEARING 4-AMINO-BENZIMIDAZOLE LIGANDS FOR MAKING POLY(ETHYLENE-CO-1-ALKENE)CROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U. S. Provisional Application Serial No. 63 / 765,194 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 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-phase 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 the diluent and the unreacted reactants, with the diluent and unreacted reactants typically being recycled86637-WO-PCT / DOW 86637 WO2back 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 catalyst systems with advantageous productivity, efficiency, operability, and resultant polymer properties relative to commercial incumbent catalyst systems. For example, 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 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 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 catalyst systems employing Group IV heteroleptic amidine complexes bearing a 4-amino-benzimidazole ligand have high activity and are capable of producing poly(ethylene-co-l -alkene) copolymers via solution-phase polymerization with low comonomer incorporation (e.g., less than or equal to 1 wt% comonomer) and high weight-average molecular weight (e.g., greater than 450,000 g / mol). The high activity in combination with the high Mwand low comonomer incorporation of the poly(ethylene-co-l -alkene) copolymers produced using the catalyst systems described herein shows that the catalyst systems of the present disclosure are 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 solution-phase polymerization processes.

[0008] Embodiments of this disclosure include catalyst systems comprising heteroleptic 4-amino-benzimidazole amidine complexes, and methods of making a poly(ethylene-co-l -alkene) copolymer that include polymerizing, via solution-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of the catalyst systems disclosed herein.86637-WO-PCT / DOW 86637 WO3

[0009] According to a first aspect of the present disclosure, a catalyst system comprises a metalligand 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 independently selected 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 (C6-C3o)aryl.86637-WO-PCT / DOW 86637 WO4

[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 / / z -substituents.

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

[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):86637-WO-PCT / DOW 86637 WO

[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.

[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.86637-WO-PCT / DOW 86637 WO6

[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] According to a twenty-sixth aspect of the present disclosure, a method of making an ethylene-based polymer comprises polymerizing, via solution-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of the catalyst system of any one of the first through twenty-fifth aspects.

[0037] A twenty-seventh aspect includes the twenty-sixth aspect, wherein the method comprises polymerizing the combination of ethylene monomer and at least one 1 -alkene comonomer.

[0038] A twenty-eighth aspect includes the twenty-seventh aspect, wherein the at least one 1 -alkene comonomer comprises 1 -octene.

[0039] 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

[0040] 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, embodiments86637-WO-PCT / DOW 86637 WO7are 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.

[0041] Common abbreviations are listed below:

[0042] R, Q, M, X and n: as defined above; Me: methyl; Et: ethyl; Ph: phenyl; Bn: benzyl; Cy: cyclohexyl; iPr: z o -propyl; nBu: zz-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;N3SiMe3or TMS-N3: trimethylsilyl azide; ZrBn4: zirconium(IV) tetrabenzyl; Cy3PNH: tricyclohexyl-phosphinimine; CpZrBn3: cyclopentadienylzirconium(IV) tribenzyl; CpZrCl3: cyclopentadienylzirconium(IV) trichloride; Cy3PNZrBn3: tricyclohexyl-phosphinimidezirconium(IV) tribenzyl; (amid-Ph)ZrBn3: AW-di-z o-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 RIBS-II: bis(hydrogenated tallow alkyljmethyl, 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.

[0043] 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.

[0044] 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 that86637-WO-PCT / DOW 86637 WO8participates 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.

[0045] 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.

[0046] 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 that converts the procatalyst to a catalytically active catalyst. As used herein, the term “activating cocatalyst” and “activator” are interchangeable terms.

[0047] 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.

[0048] 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 of86637-WO-PCT / DOW 86637 WO9various compounds, “hydrogen” and “-H” are interchangeable, and unless clearly specified have identical meanings.

[0049] 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-Cio)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)).

[0050] 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.

[0051] 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 is86637-WO-PCT / DOW 86637 WO10present, 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 (Ce-Cisjaryl; 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 (Ce-Cisjaryl; 2,4-bis([C2o]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-l-yl.

[0052] 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., (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.

[0053] 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.

[0054] 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 alkylenee 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_, -(CEE)?-, -(CEEje-, -(CEE)?-, -(CEEjs-, - CH2C*HCH3, and -(CH2)4C*(H)(CH3), in which “C*” denotes a carbon atom86637-WO-PCT / DOW 86637 WO11from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (Ci-C5o)alkylene are substituted (Ci-C2o)alkylene, -CF2-, -C(O)-, and - (CH2)i4C(CH3)2(CH2)5_(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-C5o)alkylene 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.

[0055] The term “(C3-C5o)cycloalkylene” 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. Other cycloalkylene 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.

[0056] 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-Cis)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.86637-WO-PCT / DOW 86637 WO12

[0057] 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)-, (Ci-C5o)hydrocarbyl-S(0)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.

[0058] 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)-, (Ci-C3o)hydrocarbyl-S(0)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.

[0059] 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.

[0060] 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;86637-WO-PCT / DOW 86637 WO13oxazol-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 is l,7-dihydropyrrolo[3,2-f] indol-l-yl. An example of the fused 5, 6,6-ring system is lH-benzo[f] indol-l-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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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").

[0065] The term “saturated” means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorous, and carbon-86637-WO-PCT / DOW 86637 WO14silicon 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.

[0066] Embodiments of the catalyst systems described herein include a metal-ligand complex having a structure according to Formula (I):

[0067] 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 connected86637-WO-PCT / DOW 86637 WO15to 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.

[0068] 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 (Ce-C3o)aryl. In some specific examples, M is zirconium.

[0069] 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.

[0070] 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 (C1-C10)alkyl ortho-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 (C1-C10)alkyl ortho-substituents, the catalysts systems described herein are able to produce poly(ethylene-co-l -alkene) copolymers having high Mw(e.g., greater than 450,000 g / mol or greater than 900,000 g / mol) and low comonomer incorporation (e.g., less than or equal to 1.0 wt%), while also achieving high activity under commercially relevant process conditions. In some specific examples, R1is 2,6-dimethylphenyl or 2,6-di(iso-propyl)phenyl.

[0071] 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.

[0072] In some example metal-ligand complexes according to Formula (I), R5is (Ci-Cio)alkyl or (C6-C2o)aryl. In some specific examples, R5is 4-butylphenyl.

[0073] In some example metal-ligand complexes according to Formula (I), R2, R3, and R4are -H.

[0074] In some examples of the catalyst systems described herein, the metal-ligand complex has a structure according to Formula (II):86637-WO-PCT / DOW 86637 WO16R81TX r9NM^X)n (II)R6\\ V zN" R1R5R3

[0075] 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.

[0076] 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.

[0077] In some example metal-ligand complexes according to Formula (II), R8and R9are independently (Ci-Cio)alkyl. In some specific examples, R8and R9are isopropyl.

[0078] 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.

[0079] 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, or86637-WO-PCT / DOW 86637 WO17(Ci-C2o)heterohydrocarbyl and each RKand RLis independently hydrogen, (Ci-C2o)hydrocarbyl, or (Ci-C2o)heterohydrocarbyl.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] In some examples of the 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-386637-WO-PCT / DOW 86637 WO18

[0084] In some specific examples, the metal-ligand complex of the catalyst systems described herein is IMLC-2 or IMLC-3.Co-catalyst Component

[0085] In some examples of the present disclosure, the catalyst system may include a co-catalyst component. In some examples, the co-catalyst component includes one or more activating cocatalysts (also referred to herein as “activators”) and the catalyst system comprising a metal-ligand complex of Formula (I) may be rendered catalytically active by any technique known in the art for activating metal -based catalysts of olefin polymerization reactions. For example, the metal-ligand complex according to Formula (I) may be rendered catalytically active by contacting the metalligand complex to, or combining the metal-ligand complex with, one or more activating co-catalysts (also referred to herein as an “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 activating co-catalysts 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 activating co-catalysts 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. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0086] Lewis acid activating co-catalysts 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 activating co-catalyst is a tris((Ci-C2o)hydrocarbyl borate (e.g. trityl tetrafluoroborate) or a86637-WO-PCT / DOW 86637 WO19tri((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.

[0087] Combinations of neutral Lewis acid activating co-catalysts 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.

[0088] Exemplary suitable activating co-catalysts 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.

[0089] In particular examples, the activating co-catalyst comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.

[0090] In particular examples, the activating co-catalyst comprises unsubstituted ammonium borate, a mono-substituted ammonium borate, a bi-substituted ammonium borate, a tri-substituted ammonium borate, or a tetra-substituted ammonium borate.

[0091] In particular examples, the activating co-catalyst comprises bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-) amine (RIBS-2).

[0092] In some examples, more than one of the foregoing activating co-catalysts may be used in combination with each other. A specific example of an activating co-catalyst 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 the86637-WO-PCT / DOW 86637 WO20activating co-catalysts is 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 activating co-catalyst, preferably the number of moles of the alumoxane that are employed is at least 100 times the number of moles of the metalligand complex of Formula (I). When tris(pentafluorophenyl)borane alone is used as the activating co-catalyst, 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 activating co-catalysts are generally employed in approximately mole quantities equal to the total mole quantities of one or more metal-ligand complexes of Formula (I).

[0093] In some examples, when more than one of the foregoing co-catalyst components is used in combination, one or more of the co-catalyst components may function as a scavenger. The purpose of the scavenger is to react with any water or other impurities present in the system that might otherwise react with the catalyst leading to reduced efficiency. In embodiments, the catalyst systems described herein may include an activator or both an activator and a scavenger.

[0094] In some examples, the co-catalyst component includes an activator comprising unsubstituted ammonium borate, a mono-substituted ammonium borate, a bi-substituted ammonium borate, a tri-substituted ammonium borate, or a tetra-substituted ammonium borate, and a scavenger comprising methylaluminoxane (MAO), modified methyl aluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.

[0095] In some embodiments, the co-catalyst component includes an activator comprising 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.Polymerization Processes

[0096] As noted above, embodiments of this disclosure include polymerization processes. The polymerization processes may include polymerizing, in a polymerization reactor, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of a catalyst system described herein comprising a metal-ligand complex according to Formula (I). Any conventional polymerization processes may be employed to produce the ethylene-based polymers. Such conventional polymerization processes include, but are not limited to, solution-phase86637-WO-PCT / DOW 86637 WO21polymerization processes, gas-phase polymerization processes, slurry-phase polymerization processes, and combinations thereof using one or more conventional reactors such as loop reactors, isothermal reactors, fluidized bed gas-phase reactors, stirred tank reactors, batch reactors in parallel, series, or any combinations thereof, for example.

[0097] In particular examples the ethylene-based polymer may be produced via solution-phase polymerization. In some examples, the ethylene-based polymer may be produced via solution-phase polymerization using one or more loop reactors, isothermal reactors, and combinations thereof. In some examples, the solution-phase polymerization process occurs in one or more well-stirred reactors such as one or more loop reactors or one or more spherical isothermal reactors at a temperature in the range of from 120 to 300 °C; for example, from 120 °C to 190 °C, from 110 °C to 160 °C, or from 120 °C to 150 °C, and at pressures in the range of from 200 to 1500 psi; for example, from 200 to 750 psi or 200 to 500 psi. In some examples, the ethylene-based polymer may be produced via solution-phase polymerization at a polymerization temperature of between 110 and 130 °C, or between 115 and 125 °C. In some examples, the ethylene-based polymer may be produced via solution-phase polymerization at a polymerization temperature of between 140 and 160 °C, or between 145 and 155 °C. The residence time in solution-phase polymerization process is typically in the range of from 2 to 30 minutes; for example, from 10 to 20 minutes. Ethylene, one or more solvents, one or more catalyst systems, such as catalyst system that includes a metal-ligand complex according to Formula (I), optionally one or more co-catalyst components, and optionally one or more comonomers are fed continuously to the one or more reactors. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents are commercially available under the name ISOPAR E from ExxonMobil Chemical Co., Houston, Texas. 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.

[0098] In some examples, the ethylene-based polymer may be produced via solution-phase polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and optionally one or more a-olefins are polymerized in the presence of the catalyst system, as described herein, and optionally one or more co-catalysts. In another embodiment, the ethylene-based polymer may be produced via solution-phase polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and optionally one or more a-olefins are polymerized in86637-WO-PCT / DOW 86637 WO22the presence of the catalyst system in this disclosure. The catalyst system, as described herein, can be used in the first reactor, or second reactor, optionally in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer may be produced via solution-phase polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and optionally one or more a-olefins are polymerized in the presence of the catalyst system, as described herein, in both reactors.

[0099] In another embodiment, the ethylene-based polymer may be produced via solution-phase polymerization in a single reactor system, for example, single loop reactor system, in which ethylene and optionally one or more a-olefins are polymerized in the presence of the catalyst system, as described within this disclosure, and optionally one or more co-catalyst components, as described in the preceding paragraphs.

[0100] In one or more embodiments, the polymerization process using the catalyst systems described herein produces greater than or equal to 10,000 grams of the ethylene-based polymer per grams of the metal (gpoly / gmetal) of the metal-ligand complex. In some embodiments, the polymerization process produces greater than or equal to 50,000 gpoly / gmetal, greater than or equal to 100,000 gpoly / gmetal, greater than or equal to 200,000 gpoly / gmetal, greater than or equal to 300,000 gpoly / gmetal, greater than or equal to 400,000 gpoly / gmetal, greater than or equal to 500,000 gpoly / gmetal, greater than or equal to 600,000 gpoly / gmetal, greater than or equal to 700,000 gpoly / gmetal, greater than or equal to 800,000 gpoly / gmetal, greater than or equal to 900,000 gpoly / gmetal, greater than or equal to 1,000,000 gpoly / gmetal, greater than or equal to 1,100,000 gpoly / gmetal, greater than or equal to 1,200,000 gpoly / gmetal, greater than or equal to 1,300,000 gpoly / gmetal, greater than or equal to 1,400,000 gpoly / gmetal, greater than or equal to 1,500,000 gpoly / gmetal, greater than or equal to 1,600,000 gpoly / gmetal, greater than or equal to 1,700,000 gpoly / gmetal, greater than or equal to 1,800,000 gpoly / gmetal, greater than or equal to 1,900,000 gpoly / gmetal, or even greater than or equal to 2,000,000 gpoly / gmetal.Polyolefins

[0101] The catalytic systems described in the preceding paragraphs are utilized in the polymerization of olefin-based polymers. While the catalytic systems of this disclosure are utilized in the polymerization of ethylene, it should be understood that such catalytic 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-olefm) in the polymerization scheme, creating a homopolymer. However, additional a-olefins may be incorporated into the polymerization procedure. The additional86637-WO-PCT / DOW 86637 WO23ot-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 ot-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 ot-alkene comonomer is 1 -octene.

[0102] The ethylene-based polymers, for example homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as ot-olefins, 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 “from at 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).

[0103] In some embodiments, the ethylene-based polymers polymerized in the presence of a catalyst system described herein may comprise at least 85 mole percent (mol%) units derived from ethylene. All individual values and subranges from at least 85 mol% are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymers may comprise at least 87 mol% units derived from ethylene, at least 90 mol% units derived from ethylene, at least 93 mol% units derived from ethylene, at least 95 mol% units derived from ethylene, at least 96 mol% units derived from ethylene, at least 97 mol% units derived from ethylene, at least 98 mol% units derived from ethylene, at least 99 mol% units derived from ethylene, or at least 99.5 mol% units derived from ethylene. In embodiments, the ethylene-based polymers may comprise from 85 to 100 mol% units derived from ethylene, from 90 to 100 mol% units derived from ethylene, from 9386637-WO-PCT / DOW 86637 WO24to 100 mol% units derived from ethylene, from 95 to 100 mol% units derived from ethylene, from 97 to 100 mol% units derived from ethylene, from 98 to 100 mol% units derived from ethylene, from 99 to 100 mol% units derived from ethylene, or from 99.5 to 100 mol% units derived from ethylene. In embodiments, the ethylene-based polymers may comprise from 85 to 99.9 mol% units derived from ethylene, from 87 to 99.9 mol% units derived from ethylene, from 90 to 99.9 mol% units derived from ethylene, from 93 to 99.9 mol% units derived from ethylene, from 95 to 99.9 mol% units derived from ethylene, from 97 to 99.9 mol% units derived from ethylene, from 99 to 99.9 mol% units derived from ethylene, or from 99.5 to 99.9 mol% units derived from ethylene.

[0104] In embodiments, the ethylene-based polymers polymerized in the presence of a catalyst system described herein may have a comonomer incorporation of greater than or equal to 0.1 mol% and less than or equal to 15 mol%, greater than or equal to 0.1 mol% and less than or equal to 13 mol%, greater than or equal to 0.1 mol% and less than or equal to 10 mol%, greater than or equal to 0.1 mol% and less than or equal to 7 mol%, greater than or equal to 0.1 mol% and less than or equal to 6 mol%, greater than or equal to 0.1 mol% and less than or equal to 5 mol%, greater than or equal to 0.1 mol% and less than or equal to 4 mol%, greater than or equal to 0.1 mol% and less than or equal to 3 mol%, greater than or equal to 0.1 mol% and less than or equal to 2 mol%, greater than or equal to 0.1 mol% and less than or equal to 1 mol%, or greater than or equal to 0.5 mol% and less than or equal to 1 mol%.

[0105] In some embodiments, the ethylene-based polymers polymerized in the presence of a catalyst system described herein may have a weight-average molecular weight of greater than or equal to 10,000 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 catalyst system described herein may have a weight-average molecular weight of greater than or equal to 20,000 g / mol, greater than or equal to 30,000 g / mol, greater than or equal to 40,000 g / mol, greater than or equal to 50,000 g / mol, greater than or equal to 60,000 g / mol, greater than or equal to 70,000 g / mol, greater than or equal to 80,000 g / mol, greater than or equal to 90,000 g / mol, 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 450,000 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, or even greater than or equal to 1,000,000 g / mol.86637-WO-PCT / DOW 86637 WO25

[0106] In some embodiments, the ethylene-based polymers polymerized in the presence of a catalyst system described herein may have a polydispersity index (PDI) from 1 to 200, where PDI is 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 4 to 50, from 4 to 20, from 5 to 50, from 5 to 20, from 6 to 50, from 6 to 20, from 7 to 50, from 7 to 20, from 8 to 50, from 8 to 20, from 9 to 50, from 9 to 20, or from 9 to 15.

[0107] In some embodiments, the ethylene-based polymers polymerized in the presence of a catalyst system described herein may have a melt temperature (Tm) of at least 80 °C, at least 85 °C, at least 90 °C, at least 95 °C, at least 100 °C, at least 105 °C, at least 110 °C, at least 115 °C, or at least 119 °C. In some examples, the ethylene-based polymers polymerized in the presence of a catalyst system described herein may have a melt temperature (Tm) from 100 °C to 130 °C, from 105 °C to 130 °C, from 110 °C to 130 °C, from 115 °C to 130 °C, from 119 °C to 130 °C, or from 119 °C to 125 °C.

[0108] 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 fillers, which may include, but are not limited to, organic or inorganic fillers. The ethylene-based polymers may contain from about 0 to about 20 weight percent fillers such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the combined weight of the ethylene-based polymers and all additives or fillers. The ethylene-based polymers may further be blended with one or more polymers to form a blend.

[0109] Embodiments of the 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.86637-WO-PCT / DOW 86637 WO26Measurement StandardsMelt Temperature

[0110] Melt temperature (Tm) is measured by differential scanning calorimetry (DSC2500 or Discovery DSC, TA Instruments, Inc.) using a heat-cool-heat temperature profile. Samples of 3-6 mg are loaded in open aluminum pans and temperature equilibration is achieved at 200 °C. After being held at this temperature for 2 minutes, the samples are cooled to -90 °C at 10 °C / min. After being held at -90°C for 4 minutes, the samples are then heated to 200 °C at 10 °C / min. Traces of the second heat cycle are analyzed individually using TA Trios software.HT-GPC Analysis with IR Detection of Octene Incorporation

[0111] Mw, Mn, and Polydispersity Index (Mw / Mn) are 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.

[0112] 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 μm (50 x 7.5 mm) guard column followed by two PL-gel 20 μm (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 weight Agilent EasiCal polystyrene standards (PS-1 and PS-2) are diluted with 1.5 mL of TCB stabilized with BHT and dissolved by stirring at 160 °C for 15 minutes. The PS standards are injected into the system without further dilution to create a third-order Mwcalibration curve with apparent units adjusted to homo-polyethylene (PE) using known Mark-Houwink coefficients for PS and PE. Octene incorporation is determined using a linear calibration developed by analyzing copolymers of known compositions.

[0113] One or more features of the present disclosure are illustrated in view of the examples as follows:EXAMPLES

[0114] All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexanes, tetrahydrofuran, and diethyl ether were purified86637-WO-PCT / DOW 86637 WO27via 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 and 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 μm 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.

[0115] 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 forNMR 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 withdecoupling, 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).

[0116] 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). In Example 17, the results of Batch Reactor Polymerization Tests are tabulated and discussed.Synthesis of Precursor Compounds for 4-Amino-Benzimidazole LigandsExample 13-bromo-N-(4-butylphenyl)-2-nitroanilineBr NO2I IzHH2NX[ / ^1 +JX. NO2 >DMSOF 130 °C / 15 h86637-WO-PCT / DOW 86637 WO28

[0117] 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 %.

[0118] 'H NMR (400 MHz, CDCI3) 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).

[0119] 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

[0120] 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 through Celite, then the organic layer was collected and purified by column chromatography (90:10 Hex: EtOAc). Yield = 1.10 g, 93%.

[0121] 1H NMR (400 MHz, CDCI3) 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).

[0122] 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, 14.02.86637-WO-PCT / DOW 86637 WO29Example 34-bromo-l-(4-butylphenyl)-2-(o-tolyl)-lH-benzo[d]imidazole1. EtOH 2. I2 / K2CO3CH2CI2

[0123] 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%.

[0124] '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).

[0125] 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.CM3 Synthesis General Procedure

[0126] 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.

[0127] 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 saturated86637-WO-PCT / DOW 86637 WO30aqueous 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 fdter 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.

[0128] Preparative SFC was carried out using a 1-AA 130 Å 5 μm 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.Synthesis of 4-Amino-Benzimidazole LigandsExample 4Ligand 1 (L-l)

[0129] Ligand 1 was prepared using the CM3 Synthesis General Procedure.

[0130] 'H NMR (400 MHz, CDCI3) 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).86637-WO-PCT / DOW 86637 WO31

[0131] 13C NMR (101 MHz, CDCl₃) δ 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

[0132] Ligand 2 was prepared using the CM3 Synthesis General Procedure.

[0133] 'H NMR (400 MHz, CDCl3) δ 7.44 - 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,. / = 7.3 Hz, 3H).

[0134] 13C NMR (101 MHz, CDCl₃) δ 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

[0135] Ligand 3 was prepared using the CM3 Synthesis General Procedure.86637-WO-PCT / DOW 86637 WO

[0136] 'H NMR (400 MHz, CDCl₃) δ 7.46 - 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).

[0137] 13C NMR (101 MHz, CDCl₃) δ 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 7AW-diisopropylbenzimidamideMeMgBrNToluener.t., 16 h

[0138] 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 stirring for 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 %.

[0139] 'H NMR (300 MHz; CDCl₃) δ 7.42 - 7.22 (m, 5H), 5.85 (s, 2H), 2.97 (m, 2H), 1.09 (d, 12H).86637-WO-PCT / DOW 86637 WO33Example 8(amid-Ph)ZrBii3Bni Toluene ZrBn i BnBn r.t., 1 h

[0140] 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.

[0141] '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).

[0142] 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

[0143] 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 of amidine 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 forpolymerization testing.86637-WO-PCT / DOW 86637 WO34Synthesis of Inventive Metal-Ligand ComplexesExample 9IMLC-1

[0144] 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.

[0145] '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

[0146] 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.

[0147] '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: Resonances 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

[0148] 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.86637-WO-PCT / DOW 86637 WO35

[0149] ¹H NMR (500 MHz, C6D6) 87.75 (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)

[0150] The structures of comparative metal-ligand complexes CMLC-2 and CMLC-3 are shown below:CMLC-2Example 12CpZrBns3.15 equiv BnMgCIcr i "cici Toluene-25 °C to r.t., 1 h

[0151] In a glovebox, CpZrCft (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 gradually86637-WO-PCT / DOW 86637 WO36turned 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

[0152] 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 CpZrBns as the metal precursor.

[0153] '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 = 10.7 Hz, 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 (CysPNH)NjSiMej MeOH NHIIToluene Toluene Cy i Cy85 °C, 18 h Cy i CyCy 40 °C, 12 h Cy

[0154] 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 1886637-WO-PCT / DOW 86637 WO37h. 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^CyBnI Toluene IIp'ii Zr\ N NH Bn I BnBn r.t., 18 h ZrBnZI BnBn

[0155] 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. ¹H NMR (400 MHz, C₆D₆) 8 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, C6D6) 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

[0156] 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 Cy3PNZrBn3as the metal precursor.

[0157] '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,86637-WO-PCT / DOW 86637 WO3818H), 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 17Polymerization ReactionsBatch Reactor Polymerization Procedure

[0158] The batch reactor polymerizations were conducted in a 2-L Parr™ batch reactor. The reactor is heated by an electrical heating mantle, and is cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating / cooling system are controlled and monitored by a Camile™ TG process computer. The bottom of the reactor is fitted with a dump valve, which empties the reactor contents into a stainless-steel dump pot, which is prefilled with a catalyst kill solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). The dump pot is vented to a 30-gal. blow-down tank, with both the pot and the tank purged with nitrogen. All solvents used for polymerization or catalyst makeup are run through solvent purification columns to remove any impurities that may affect polymerization. The 1 -octene and Isopar E were passed through two columns, the first containing activated A2 alumina, the second containing activated Q5 reactant. The ethylene was passed through two columns, the first containing A204 alumina and 4A mol sieves, the second containing Q5 reactant. The N2, used for transfers, was passed through a single column containing A204 alumna, 4 A mol sieves and Q5.

[0159] The reactor is loaded first from the shot tank that contains Isopar E solvent and / or 1 -octene, depending on desired reactor loading. The shot tank is filled to the load set points by use of a lab scale to which the shot tank is mounted. After liquid feed addition, the reactor is heated up to the polymerization temperature set point. If ethylene is used, it is added to the reactor when at reaction temperature to maintain reaction pressure set point. Ethylene addition amounts are monitored by a micro-motion flow meter.

[0160] The catalyst and activators were mixed with the appropriate amount of purified toluene to achieve a solution of the desired molarity. The catalyst and activators were handled in an inert glove box, drawn into a syringe and pressure transferred into the catalyst shot tank. This was followed by three rinses of toluene, 5-mL each. Immediately after catalyst addition the run timer began. If ethylene was used, it was then added by the Camile to maintain reaction the pressure set point in the reactor. These polymerizations were run for 10 min., then the agitator was stopped and the bottom dump valve was opened to empty reactor contents into the dump pot. The dump pot contents were86637-WO-PCT / DOW 86637 WO39poured into trays placed in a lab hood where the solvent was evaporated off overnight. The trays containing the remaining polymer were then transferred to a vacuum oven, where they were heated up to 140 °C under vacuum to remove any remaining solvent. After the trays cooled to ambient temperature, the polymers were weighed for yield / efficiencies, and submitted for polymer testing.

[0161] Table 1 presents results of polymerization reactions for inventive metal-ligand complexes IMLC-1 to IMLC-3 following the Batch Reactor Polymerization Procedure disclosed herein. Table 2 presents results of polymerization reactions for comparative metal-ligand complexes CMLC-2 and CMLC-3 following the Batch Reactor Polymerization Procedure disclosed herein. The reactor conditions for the results presented in Tables 1 and 2 for the polymerization reactions at 120 °C include 46.3 g of ethylene, 302 g of 1-octene, 612 g of Isopar E, 1.2 eq. of RIBS-2 activator with respect to catalyst, 10 pmol of MMA0-3A, and 290 psi reactor pressure. The reactor conditions for the results presented in Tables 1 and 2 for the polymerization reactions at 150 °C include 43 g of ethylene, 301 g of 1-octene, 548 g of Isopar E, 1.2 eq. of RIBS-2 activator with respect to catalyst, 10 pmol of MMA0-3A, and 327 psi reactor pressure.TABLE 1: Batch reactor results for ethylene-octene copolymerization reactions using inventive heteroleptic 4-amino-benzimidazole complexes (IMLC-1 to IMLC-3) Metal- Efficiency Catalyst PDITemp Yield M Tn. Octene Ligand (g poly / Loadingw(Mw / (°C) (g) (g / mol) (°C) (mol%) Complex g metal) (pmol) Mn)IMLC-1 120 602,912 11.0 0.20 1,012,314 9.9 120.6 0.5 IMLC-1 150 227,462 8.3 0.40 527,258 9.6 119.0 0.7 IMLC-2 120 2,027,975 18.5 0.10 1,053,696 4.8 121.3 0.4 IMLC-2 150 915,329 16.7 0.20 635,163 8.5 122.1 1.0 IMLC-3 120 1,666,228 15.2 0.10 942,656 14.1 120.9 0.7IMLC-3 150 400,114 7.3 0.20 474,382 17.9 119.7 0.986637-WO-PCT / DOW 86637 WO40TABLE 2: Batch reactor results for ethylene-octene copolymerization reactions using comparative heteroleptic 4-amino-benzimidazole complexes (CMLC-2 and CMLC-3)Metal- Efficiency Catalyst PDITemp Yield M Tn. Octene Ligand ( Loadingwg poly / (Mw / (g / mol) (mo Comp (°C) (g) (°C) l%) lex g metal) (pmol) Mn)CMLC-2 120 197,316 1.8 0.10 392,630 6.5 104.3 8.0 CMLC-2 150 32,886 0.9 0.30 153,546 7.1 105.3 9.3 CMLC-3 120 635,798 5.8 0.10 400,971 4.5 120.1 1.2 CMLC-3 150 208,279 3.8 0.20 201,854 5.4 118.7 1.4

[0162] The solution reactor results for the inventive metal-ligand complexes IMLC-1 through IMLC-3, which are group (IV) amidine complexes bearing 4-amino-benzimidazole ligands with differentiated substituents on the organometallic complex framework, are shown in Table 1. The solution reactor results for comparative examples CMLC-2 and CMLC-3, which are group (IV) complexes bearing the same 4-amino-benzimidazole ligands but alternative spectator ligands, such as cyclopentadienyl or phosphinimide ligands (CMLC-2 and CMLC-3, respectively), is shown in Table 2. As can be seen, the inventive examples demonstrate comparable or higher efficiency than the comparative examples, and in some cases, significantly higher efficiency. For example, the inventive examples IMLC-2 and IMLC-3 exhibit efficiencies at 120 °C of 2.0x106g poly / g metal and 1.7×106g poly / g metal, respectively, where the comparative examples CMLC-2 and CMLC-3 exhibit efficiencies at 120 °C of 0.2x106g poly / g metal and 0.6x106g poly / g metal, respectively. Similarly, at a polymerization temperature of 150 °C, the inventive examples IMLC-2 and IMLC-3 exhibit efficiencies of 0.9x106g poly / g metal and 0.4x106g poly / g metal, respectively, where the comparative examples CMLC-2 and CMLC-3 exhibit efficiencies of 0.03×106g poly / g metal and 0.2x106g poly / g metal, respectively.

[0163] Additionally, the inventive heteroleptic 4-amino-benzimidazole amidine complexes produce polymers with higher weight-average molecular weights (Mw) and lower comonomer incorporation. Accordingly, the solution reactor results presented herein clearly demonstrate how having both a 4-amino-benzimidazole ligand and an amidine spectator ligand on the group (IV) metal center imparts desirable olefin polymerization properties relative to other heteroleptic 4-amino-benzimidazole complexes. Moreover, the high activity combined with high Mwcapability and high ethylene selectivity (i.e., low octene mol% in copolymer) achieved by the catalyst systems described86637-WO-PCT / DOW 86637 WO41herein shows that the catalyst systems of the present disclosure may be used to produce resins with potential advantageous properties for both single and multi-catalyst applications.

[0164] 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.

[0165] 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.

[0166] 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.”

[0167] 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.

[0168] 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 ranges86637-WO-PCT / DOW 86637 WO42formed from all stated quantitative values of a given property or measurement are contemplated in this disclosure.

[0169] 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

86637-WO-PCT / DOW 86637 WO43CLAIMS1. A catalyst system comprising 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 and86637-WO-PCT / DOW 86637 WO44Sub2are 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 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, -(CH?)wSi(Rx)3, and halogen; andR1is (Ci-C3o)alkyl or (Ce-C3o)aryl.3 The catalyst system of either one of claims 1 or 2, wherein R1is 2-methylphenyl, 26-dimethylphenyl, or 2,6-di(iso-propyl)phenyl.4 The catalyst system of any one of claims 1 to 3, wherein R6is (C6-C?o)aryl or (C3-C2o)cycloalkyl.5 The catalyst system of any one of claims 1 to 4, wherein R6is 2-methylphenyl.6 The catalyst system of any one of claims 1 to 5, wherein R5is (Ci-Cio)alkyl or (C6-C?o)aryl.7 The catalyst system of any one of claims 1 to 6, wherein R5is 4-butylphenyl.8 The catalyst system of any one of claims 1 to 7, wherein R2, R3, and R4are -H.9 The catalyst system of any one of claims 1 to 8, wherein the metal-ligand complex has a structure according to Formula (II):86637-WO-PCT / DOW 86637 WO45where: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 catalyst system of claim 9, wherein R7is unsubstituted phenyl.

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

12. The 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 catalyst system of any one of claims 1 to 12, wherein each X is benzyl.

14. The 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-3:86637-WO-PCT / DOW 86637 WO4615. A method of making an ethylene-based polymer, the method comprising:polymerizing, via solution-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of the catalyst system of any one of claims 1 to 14.

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