Polymerization processes that include group-iii metal and lanthanide ANSA-metallocene metal-ligand complexes

Abstract

Catalyst systems for the polymerization of ethylene-based polymers include an ansa-metallocene catalyst with a metal center, where the metal center is scandium, yttrium, or a lanthanide. Methods of making an ethylene-based polymer include polymerizing, in a polymerization reactor, ethylene, or a combination of ethylene and at least one α-olefin, in the presence of a catalyst system comprising a metal-ligand complex according to Formula (I).

Description

86265-WO-PCT / DOW 86265 WO1POLYMERIZATION PROCESSES THAT INCLUDE GROUP III METAL AND LANTHANIDE ANSA-METALLOCENE METAL-LIGAND COMPLEXESCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U. S. Provisional Application Serial No.63 / 730,591 filed December 11, 2024, the contents of which are incorporated in their entirety herein.TECHNICAL FIELD

[0002] The present disclosure is generally directed to olefin polymerization catalyst systems and processes and, more specifically, to catalyst systems including an ansa-metallocene metal-ligand complex with a Group III or lanthanide metal center and olefin polymerization processes incorporating the same.BACKGROUND

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

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

[0005] The catalyst systems for producing ethylene-based polymers typically include a chromium-based catalyst system, a Ziegler-Natta catalyst system, and / or a molecular (either metallocene or non-metallocene) catalyst system. The reactants and the catalyst system are circulated at an elevated polymerization temperature around the reactor, thereby producing ethylene-based homopolymer or copolymer. Either periodically or continuously, part of the86265-WO-PCT / DOW 86265 WO2reaction 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 recycled back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor, serially connected to the first reactor, where a second polyethylene fraction may be produced.SUMMARY

[0006] The development of Group III metal and lanthanide-based bis-phenyl-phenoxy catalyst systems has led to a step change in ethylene selectivity, enabling advanced dual reactor polymer designs. Moreover, the ability to control molecular weight and efficiency has allowed for the broad applicability of these ethylene-selective catalyst systems. Metallocene catalysts have been effective in gas- and solution-phase polyethylene production. With the simplicity of metallocene ligands compared to bis-phenyl-phenoxy ligands, it would be advantageous to develop metallocene catalysts that show similar ethylene selectivity and efficiency improvements as observed for bis-phenyl-phenoxy catalyst systems. However, current research efforts directed to metallocene catalysts for the production of ethylene-based polymers are typically limited to Zr-, Hf-, or Ti-based complexes, and research efforts extended to Group III metal and lanthanide-based metallocene catalyst systems are typically limited to bis-metallocene catalyst systems. Accordingly, there is a need to develop Group III metal and lanthanide-based ansa-metallocene catalyst systems and polymerization methods using the same.

[0007] The present disclosure is directed to methods of making ethylene-based polymers using catalyst systems comprising Group III metal and lanthanide-based ansa-metallocene metal-ligand complexes. The present disclosure demonstrates the viability of these ansa-metallocenes in terms of their impact on molecular weight capability, ethylene selectivity, and efficiency. It has been found that catalyst systems comprising Group III metal and lanthanide-based ansa-metallocene metal-ligand complexes are able to achieve high ethylene selectivity and high activity, even at high polymerization temperatures (e.g.,86265-WO-PCT / DOW 86265 WO3> 140 °C). Accordingly, the ansa-metallocene metal-ligand complexes described herein show promise as ethylene-selective catalysts in multicatalyst systems.

[0008] Methods of making an ethylene-based polymer include polymerizing, in a polymerization reactor, ethylene, or a combination of ethylene and at least one ot-olefin, in the presence of a catalyst system comprising a metal-ligand complex according to Formula

[0009] In Formula (I), M is scandium, yttrium, or a lanthanide metal having an oxidation state of +3. X is a monodentate or bidentate ligand independently selected from unsaturated (C2–C30)hydrocarbon, unsaturated (C2–C30)heterohydrocarbon, (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, -N(RX)2, and -(CH2)wSi(Rx)3, where w is from 1 to 10, each Rxis independently selected from (Ci-C3o)hydrocarbyl and (Ci-C3o)heterohydrocarbyl, and optionally two or more Rxgroups are covalently linked. T is a Lewis base. W is carbon, silicon, or germanium. Each of R1-8is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H, wherein: optionally, R1and R2are covalently linked to form a ring; optionally, R3and R4are covalently linked to form a ring; optionally, R5and R6are covalently linked to form a ring; and optionally, R7and R8are covalently linked to form a ring. R9and R10are independently selected from (Ci-C3o)hydrocarbyl and (Ci-C3o)heterohydrocarbyl.

[0010] Catalyst systems disclosed herein include a metal-ligand complex according to Formula (I).

[0011] Some examples of catalyst systems according to Formula (I) include a metal-ligand complex according to Formula (II):86265-WO-PCT / DOW 86265 WO4

[0012] In Formula (II), X is a monodentate or bidentate ligand independently selected from unsaturated (C2–C30)hydrocarbon, unsaturated (C2~C3o)heterohydrocarbon, (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, -N(RX)2, and -(CH2)wSi(Rx)3, where w is from 1 to 10, each Rxis independently selected from (Ci-C3o)hydrocarbyl and (Ci-C3o)heterohydrocarbyl, and optionally two or more Rxgroups are covalently linked. T is a Lewis base. W is carbon, silicon, or germanium. Each of R1-8is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H, wherein: optionally, R1and R2are covalently linked to form a ring; optionally, R3and R4are covalently linked to form a ring; optionally, R5and R6are covalently linked to form a ring; and optionally, R7and R8are covalently linked to form a ring. R9and R10are independently selected from (Ci-C3o)hydrocarbyl and (Ci-C3o)heterohydrocarbyl.

[0013] Additional features and advantages of the technology disclosed herein will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the technology as described herein, including the detailed description and claims which follow.

[0014] 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

[0015] Exemplary features of methods of making an ethylene-based polymer will now be described. It should be understood that the methods and catalyst systems of this disclosure may be embodied in different forms and should not be construed as limited to the specific86265-WO-PCT / DOW 86265 WO5embodiments set forth in this disclosure. Rather, embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0016] Common abbreviations are listed below:

[0017] R, M, W, T, and X: as defined above; Me: methyl; Et: ethyl; Ph: phenyl; n-BuLi: 77-butyl lithium; TEA: triethylaluminum; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; LiCEhTMS: (trimethylsilyl)methyllithium; TMS: trimethylsilyl;ScCh: scandium(III) chloride; N2: nitrogen gas; THF: tetrahydrofuran; Me? Si Et2O: diethyl ether; GC: gas chromatography; LC: liquid chromatography; RIBS-2: bis(hydrogenated tallow alkyljmethyl, tetrakis(pentafluorophenyl)borate(l-) amine; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimoles; g: gram; mL: milliliters; M: molar; min or mins: minutes; h or hrs: hours; d: days; rpm: revolution per minute; rt: room temperature; Mw: weight average molecular weight; Mn: number average molecule weight.

[0018] 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.

[0019] The term “procatalyst” refers to a compound that has catalytic activity when combined with an activator. 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 co-catalyst” and “activator” are interchangeable terms.

[0020] 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-Csojalkyl 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-Csojalkyl 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 or86265-WO-PCT / DOW 86265 WO6more 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.

[0021] The term “substitution” means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., Rs). The term “persubstitution” means that every hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., Rs). The term “polysubstitution” means that at least two, but fewer than all, hydrogen atoms bonded to carbon atoms or heteroatoms of a corresponding unsubstituted compound or functional group are replaced by a substituent. The term “-H” means a hydrogen or hydrogen radical that is covalently bonded to another atom. When describing chemical structures of various compounds, “hydrogen” and “-H” are interchangeable, and unless clearly specified have identical meanings.

[0022] 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 non-aromatic, 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)).

[0023] The term “(Ci-C5o)alkyl” means a saturated straight or branched hydrocarbon radical of from 1 to 50 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-C5o)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.86265-WO-PCT / DOW 86265 WO7Examples 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-Cs)alkyl, respectively. Each (Ci-C5)alkyl may be methyl, trifluoromethyl, ethyl, 1 -propyl, 1-methylethyl, or 1,1 -dimethylethyl.

[0024] The term “(C6-C4o)aryl” means an unsubstituted or substituted (by one or more Rs) mono-, bi- or tricyclic aromatic hydrocarbon radical of from 6 to 40 carbon atoms, of which at least from 6 to 14 of the carbon atoms are aromatic ring carbon atoms. Other aryl groups (e.g., (Cx-Cy)aryl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs. A monocyclic aromatic hydrocarbon radical includes one aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or nonfused and aromatic or non-aromatic. Examples of unsubstituted (Ce-C4o)aryl include: unsubstituted (Ce-C2o)aryl, unsubstituted (C6-Cis)aryl; 2-(Ci-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (Ce-C4o)aryl include: substituted (Ci-C2o)aryl; substituted (C6-Cis)aryl; 2,4-bis([C2o]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-l-yl.

[0025] The term “(C3-C5o)cycloalkyl” means a saturated cyclic hydrocarbon radical of from 3 to 50 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-C4o)cycloalkyl are unsubstituted (C3-C2o)cycloalkyl, unsubstituted (C3-Cio)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3-C4o)cycloalkyl are substituted (C3-C2o)cycloalkyl, substituted (C3-Cio)cycloalkyl, cyclopentanon-2-yl, and 1 -fluorocyclohexyl.

[0026] Examples of (Ci-C5o)hydrocarbylene include unsubstituted or substituted (Ce-C5o)arylene, (C3-C5o)cycloalkylene, and (Ci-C5o)alkylene (e.g., (Ci-C2o)alkylene). The86265-WO-PCT / DOW 86265 WO8diradicals 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-l,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.

[0027] The term “(Ci-Csojalkylene” means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from 1 to 50 carbon atoms that is unsubstituted or substituted by one or more Rs. Other alkylene groups (e.g., (Cx-Cy)alkylene) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs. Examples of unsubstituted (Ci-Csojalkylene are unsubstituted (Ci-C2o)alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3), in which “C*” denotes a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (Ci-Csojalkylene are substituted (Ci-C2o)alkylene, -CF2-, -C(O)-, and -(CH2)i4C(CH3)2(CH2)s-(i.e., a 6,6-dimethyl substituted normal- 1,20-eicosylene). Since as mentioned previously two Rsmay be taken together to form a (Ci-Ci8)alkylene, examples of substituted (Ci-Csojalkylene also include l,2-bis(methylene)cyclopentane, 1,2- bis(methylene)cyclohexane, 2.3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3- bis (methylene)bicyclo [2.2.2] octane.

[0028] The term “(Cs-Csojcycloalkylene” means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more Rs. 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.

[0029] 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 Rpis86265-WO-PCT / DOW 86265 WO9unsubstituted (Ci-Ci8)hydrocarbyl or -H, and where each RNis unsubstituted (Ci-Ci8)hydrocarbyl. The term “heterohydrocarbon” refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. The term “(Ci-C5o)heterohydrocarbyl” means a heterohydrocarbon radical of from 1 to 50 carbon atoms, and the term “(Ci-C5o)heterohydrocarbylene” means a heterohydrocarbon diradical of from 1 to 50 carbon atoms. The heterohydrocarbon of the (Ci-C5o)heterohydrocarbyl or the (Ci-C5o)heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl may be on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene may be on a single carbon atom or on a single heteroatom. Additionally, one of the two radicals of the diradical may be on a carbon atom and the other radical may be on a different carbon atom; one of the two radicals may be on a carbon atom and the other on a heteroatom; or one of the two radicals may be on a heteroatom and the other radical on a different heteroatom. Each (Ci-C5o)heterohydrocarbyl and (Ci-C5o)heterohydrocarbylene may be unsubstituted or substituted (by one or more Rs), aromatic or non-aromatic, 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.

[0030] 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-Ci9)heteroaryl-(Ci-C2o)alkylene, (Ce-C2o)aryl-(C i-C i9)heteroalkylene, or (C i-C i9)heteroaryl-(C i-C2o)heteroalkylene.

[0031] 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-86265-WO-PCT / DOW 86265 WO10Cio)alkylene, (C3-C2o)cycloalkyl-(Ci-Cio)heteroalkylene, (C2-C2o)heterocycloalkyl-(Ci-Cio)heteroalkylene, (Ci-C3o)heteroaryl, (Ci-C2o)heteroaryl-(Ci-Cio)alkylene, (Ce-C2o)aryl-(Ci-Cio)heteroalkylene, or (Ci-C2o)heteroaryl-(Ci-Cio)heteroalkylene.

[0032] The term “(C3-C5o)heteroaryl” means an unsubstituted or substituted (by one or more Rs) mono-, bi-, or tricyclic heteroaromatic hydrocarbon radical of from 3 to 50 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, 3, or 4; and each heteroatom may be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol-l-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-l-yl; l,3,4-oxadiazol-2-yl; l,3,4-thiadiazol-2-yl; tetrazol- 1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1 or 2 and the heteroatoms may be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon radicals include pyridine-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical can be a fused 5,6- or 6,6-ring system. Examples of the fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radical are indol-1-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.86265-WO-PCT / DOW 86265 WO11

[0033] 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.

[0034] 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.

[0035] 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").

[0036] The term “saturated” means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorous, and carbon-silicon 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 carboncarbon double bonds, carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen, carbon-phosphorous, 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.

[0037] Methods of making an ethylene-based polymer include polymerizing, in a polymerization reactor, ethylene, or a combination of ethylene and at least one ot-olefin, in the presence of a catalyst system comprising a metal-ligand complex according to Formula (I):86265-WO-PCT / DOW 86265 WO12

[0038] In Formula (I), M is scandium, yttrium, or a lanthanide metal having an oxidation state of +3. X is a monodentate or bidentate ligand independently selected from unsaturated (C2–C30)hydrocarbon, unsaturated (C2–C30)heterohydrocarbon, (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, -N(RX)2, and -(CH2)wSi(Rx)3, where w is from 1 to 10, each Rxis independently selected from (Ci-C3o)hydrocarbyl and (Ci-C3o)heterohydrocarbyl, and optionally two or more Rxgroups are covalently linked. T is a Lewis base and is optionally covalently linked with X. W is carbon, silicon, or germanium. Each of R1-8is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H, wherein: optionally, R1and R2are covalently linked to form a ring; optionally, R3and R4are covalently linked to form a ring; optionally, R5and R6are covalently linked to form a ring; and optionally, R7and R8are covalently linked to form a ring. R9and R10are independently selected from (Ci-C3o)hydrocarbyl and (Ci-C3o)heterohydrocarbyl. The metal-ligand complex may be overall charge neutral or may have a positive charge associated with the metal center. In specific embodiments, M is scandium.

[0039] In the metal-ligand complex according to Formula (I), X may bond 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.

[0040] Examples of X as a monodentate monoanionic ligand include the monoanionic ligand being selected from hydride, (Ci-C3o)hydrocarbyl carbanion, (Ci-C3o)heterohydrocarbyl carbanion, halide, nitrate, carbonate, phosphate, sulfate, HC(O)O,86265-WO-PCT / DOW 86265 WO13HC(O)N(H)“, (Ci-C2o)hydrocarbylC(0)0, (Ci-C20)hydrocarbylC(O)N((Ci-C20)hydrocarbyl), (Ci-C2o)hydrocarbylC(0)N(H), RKRLB), RKRLN, RK0, RKS, RKRLP, or RMRKRLSi, where RK, RL, and RMare independently hydrogen, (Ci-C2o)hydrocarbyl, or (Ci-C2o)heterohydrocarbyl, or RKand RLare taken together to form a (C2-C2o)hydrocarbylene or (C2-C2o)heterohydrocarbylene and RMis independently hydrogen, (Ci-C2o)hydrocarbyl, or (Ci-C2o)heterohydrocarbyl.. 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.

[0041] Examples of X as a monodentate neutral ligand include the neutral ligand being a neutral Lewis base group such as RJNRKRI, RKORL, RKSRL, or RJPRKRI, where each RJindependently is hydrogen, [(Ci-Cio)hydrocarbyl]3Si(Ci-Cio)hydrocarbyl, (Ci-C2o)hydrocarbyl, [(Ci-Cio)hydrocarbyl]3Si, or (Ci-C2o)heterohydrocarbyl and each RKand RLindependently is independently hydrogen, (Ci-C2o)hydrocarbyl, or (Ci-C2o)heterohydrocarbyl.

[0042] In some example metal-ligand complexes according to Formula (I), X may be -(CH2)wSi(Rx)3, where w is from 1 to 10, each Rxis independently selected from (Ci-C3o)hydrocarbyl and (Ci-C3o)heterohydrocarbyl, and optionally two or more Rxgroups are covalently linked

[0043] In some example metal-ligand complexes according to Formula (I), X is (Ci-Cio)alkyl, -CH2Si[(Ci-C2o)alkyl], (Ce-C2o)aryl, or a halogen. In other example metalligand complexes according to Formula (I), X may be (Ci-Cio)alkyl or -CH2Si[(Ci-C2o)alkyl]. In other example metal-ligand complexes according to Formula (I), X may be methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro. In specific example metal-ligand complexes according to Formula (I), X may be methyl or trimethylsilyl methyl.

[0044] In the metal-ligand complex according to Formula (I), T is a Lewis base that bonds with M through a dative bond or an ionic bond. The Lewis base may be a neutral or anionic species which can donate an electron pair to an acceptor. For purposes of this description, the acceptor is M, the metal center of the metal-ligand complex of Formula (I). In some example metal-ligand complexes according to Formula (I), X and T are covalently linked. In example86265-WO-PCT / DOW 86265 WO14metal-ligand complexes according to Formula (I), the Lewis base T is a neutral hydrocarbon, an anionic hydrocarbon, a neutral heterohydrocarbon, or a monodentate neutral ligand.

[0045] An examples of a neutral hydrocarbon Lewis base includes, but is not limited to, 1,3 -butadiene. An example of an anionic hydrocarbon Lewis base includes, but is not limited to, a cyclopentadienyl ligand. In some examples, the Lewis base T does not include ethylene or an ot-olefin comonomer that may be present during polymerization.

[0046] Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cycloethers, or sulfides. In some examples, the Lewis base T may be a (Ci-C2o)heterohydrocarbon where the heteroatom is oxygen. In some examples of metal-ligand complexes according to Formula (I), T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE). In specific embodiments, T is tetrahydrofuran.

[0047] Examples of monodentate neutral ligands include, without limitation: RTNRKRL, RKORL, RKSRL, or RTPRKRL, where RTis hydrogen, [(Ci-Cio)hydrocarbyl]3Si(Ci-Cio)hydrocarbyl, (Ci-C2o)hydrocarbyl, or (Ci-C2o)heterohydrocarbyl, and where RKand RLare independently hydrogen, (Ci-C2o)hydrocarbyl, or (Ci-C2o)heterohydrocarbyl.

[0048] In the metal-ligand complex according to Formula (I), R9and R10may be independently (Ci-C2o)hydrocarbyl or (Ci-Cio)hydrocarbyl. In some examples, R9and R10may be independently (Ci-C2o)aryl. In some examples, R9and R10may be independently substituted phenyl or unsubstituted phenyl. In specific examples, R9and R10may be independently substituted phenyl.

[0049] In the metal-ligand complex according to Formula (I), R4and R8may be independently (Ci-Cio)alkyl. In specific examples, R4and R8are be methyl.

[0050] Examples of metal-ligand complexes according to Formula (I) include complexes in which R1and R2are covalently linked to form an aromatic ring, so that the metal-ligand complex according to Formula (I) has a structure according to Formula (la):86265-WO-PCT / DOW 86265 WO15

[0051] In Formula (la), M, X, T, W, and R3 10are defined as in Formula (I), and each of R11-14is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H, wherein R12and R13are optionally covalently linked to form a ring.

[0052] In some example metal-ligand complexes of Formula (la), R3and R4are covalently linked to form an aromatic ring such that the metal-ligand complex has a structure according to Formula (lb):

[0053] In Formula (lb), M, X, T, W, and R5 14are defined as in Formula (la), and each of R15-18is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H, wherein R16and R17are optionally covalently linked to form a ring. In some embodiments where the metal-ligand complex has a structure according to Formula (lb), R12and R13are covalently linked to form a non-aromatic ring and R16and R17are covalently linked to form a non-aromatic ring. In some examples, R12and R13are covalently linked to86265-WO-PCT / DOW 86265 WO16form a substituted non-aromatic ring and R16and R17are covalently linked to form a substituted non-aromatic ring. In some examples where the metal-ligand complex has a structure according to Formula (lb), at least one of R11-14may be (C4-Cio)alkyl and at least one of R15-18may be (C4-Cio)alkyl. In specific examples, at least one of R11-14and at least one of R15-18may be independently methyl, ethyl, propyl, 2-propyl, butyl, 1,1 -dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl. In specific examples, at least one of R11-14and at least one of R15-18are tert-butyl.

[0054] In further examples of metal-ligand complexes according to Formula (la), R5and R6are covalently linked to form an aromatic ring such that the metal-ligand complex has a structure according to Formula (Ic):R21

[0055] In Formula (Ic), M, X, T, W, R3, R4, and R7-14are defined as in Formula (la), and each of R19-22is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H. In some examples where the metal-ligand complex has a structure according to Formula (Ic), at least one of R11-14is (Ce-C2o)aryl and at least one of R19-22is (Ce-C2o)aryl. In specific examples, at least one of R11-14and at least one of19-22is substituted phenyl or unsubstituted phenyl. In specific examples, at least one of R11-14and at least one of R19-22is unsubstituted phenyl.

[0056] In specific examples of catalyst systems and polymerization methods described herein, the metal-ligand complex is selected from MLC-A, MLC-B, or MLC-C:86265-WO-PCT / DOW 86265 WO17MLC-A MLC-BMLC-C

[0057] Additive Component

[0058] In some embodiments, the catalyst system does not include additives. An additive is a chemical agent present during the polymerization reaction the does not deter olefin propagation. In one or more embodiments, the catalyst system further comprises an additive. In some embodiments, the additives function as a co-catalyst. In other embodiments, the additives function as a scavenger or scavenging agent. A co-catalyst is a reagent that reacts in cooperation with a catalyst to catalyze the reaction or improve the catalytic activity of the catalyst. Without intent to be bound by theory, it is believed the Lewis Base, T, of formula (I), disassociates without the presence of a co-catalyst. However, it is also believed that a co-catalyst may promote the disassociation of the Lewis base and the metal center of the metal-ligand complex.

[0059] A scavenging agent sequesters impurities in the reactor prior to addition of the precatalyst, and as such, does not constitute and activator. Lower loading of alumoxanes do not act as co-catalysts, rather they serve as scavenging agent.86265-WO-PCT / DOW 86265 WO18

[0060] Suitable additives may include, but are not limited to, alkyl aluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). Combinations of one or more of the foregoing additives 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 methylal umoxane, triisobutylal uminum-modified methylalumoxane, and isobutylalumoxane.

[0061] In some embodiments, the additive is a Lewis acid Group 13 metal compounds containing (Ci-C2o)hydrocarbyl substituents as described herein. In some embodiments, the additives include tri((Ci-C2o)hydrocarbyl)-substituted-aluminum or tri((Ci-C2o)hydrocarbyl)-boron compounds. In other embodiments, the additives are chosen from 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.

[0062] In one or more embodiments, the polymerization process further includes a borate-based additive. In some embodiments, the borate-based additive is selected from tris(fluoro-substituted phenyl)boranes, tris(pentafluorophenyl)borane. In some embodiments, the cocatalyst is a tri((Ci-C2o)hydrocarbyl)ammonium tetra((Ci-C2o)hydrocarbyl)borate (e.g. bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). 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.

[0063] In one or more embodiments, the additive may be chosen from polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as inert, compatible, noncoordinating, ion forming compounds. Exemplary suitable additives include, but are not limited to modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-)ammonium, triethyl aluminum, butylatedhydroxy-toluene diethyl aluminum, bis-(butylatedhydroxy-toluene) ethyl aluminum, tris-(butylatedhydroxy-toluene) aluminum and combinations thereof.86265-WO-PCT / DOW 86265 WO19

[0064] In some embodiments, one or more co-catalysts may be used in combination with each other. A specific example of a co-catalyst combination is a mixture of a tri((Ci-C8)hydrocarbyl)aluminum, tri((Ci-C4)hydrocarbyl)borane, tri((C6-Ci8)aryl)borane or an ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of total number of moles of one or more metal-ligand complexes of formula (I) to total number of moles of one or more of the co-catalysts is from 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments, at least 1:1000; and 10:1 or less, and in some other embodiments, 1:1 or less. When an alumoxane alone is used as the co-catalyst, preferably the ratio Al of the alumoxane and metal of the metal ligand complex of formula (I) (Al / M) is at least 20. When tris(pentafluorophenyl)borane alone is used as the 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.

[0065] Polymerization Methods

[0066] As noted above, embodiments of this disclosure include polymerization methods. The polymerization methods include polymerizing, in a polymerization reactor, ethylene, or a combination of ethylene and at least one ot-olefin, in the presence of any of the catalyst systems described herein, including catalyst systems comprising a metal-ligand complex according to Formula (I). In some embodiments, the polymerization methods include polymerizing, in a polymerization reactor, a combination of ethylene and at least one ot-olefin, in the presence of any of the catalyst systems described herein, including catalyst systems 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 polymerization 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.

[0067] In particular embodiments the ethylene-based polymer may be produced via solution polymerization. In one embodiment, the ethylene-based polymer may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system,86265-WO-PCT / DOW 86265 WO20wherein ethylene, or a combination of ethylene and at least one ot-olefin, are polymerized in the presence of the catalyst system, as described herein, and optionally one or more cocatalyst components. 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 polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene, or a combination of ethylene and at least one ot-olefin, are polymerized in the presence of the catalyst system, as described herein, in both reactors.

[0068] In another embodiment, the ethylene-based polymer may be produced via solution polymerization in a single reactor system, for example, single loop reactor system, in which ethylene, or a combination of ethylene and at least one ot-olefin, 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. In embodiments, hydrogen may be added to the reactor.

[0069] In embodiments of the methods described herein, the at least one ot-olefin may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary ot-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, the at least one ot-olefin may be selected from the group consisting of propylene, 1 -butene, 1 -hexene, and 1 -octene. In some embodiments, the at least one ot-olefin may be selected from the group consisting of 1 -hexene and 1 -octene. In specific embodiments, the at least one ot-olefin comprises 1 -octene.

[0070] As discussed above and demonstrated through the examples submitted herewith, it has been unexpectedly found that the catalyst systems described herein comprising Group III metal and lanthanide-based ansa-metallocene metal-ligand complexes are able to achieve high ethylene selectivity and high activity, even at high polymerization temperatures (e.g., > 140 °C). In embodiments, the polymerizing is performed at a polymerization temperature of at least 140 °C, at least 150 °C, at least 160 °C, at least 170 °C, at least 180 °C, or at least 190 °C.

[0071] In embodiments, the polymerization methods described herein produce at least 200,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, or at least 250,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex.86265-WO-PCT / DOW 86265 WO21In some embodiments, the polymerization methods described herein produce at least 300,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, at least 400,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, at least 500,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, at least 1,000,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, at least 2,000,000 grams of ethylene-based polymer per gram metal of the metalligand complex, at least 3,000,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, at least 4,000,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex, or at least 5,000,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex.

[0072] Polyolefins

[0073] The catalyst systems and polymerization methods described herein may be utilized to produce olefin-based polymers such as ethylene-based polymers. While the exemplary catalyst systems of this disclosure are utilized in the polymerization of ethylene-based polymers, it should be understood that such catalyst systems may be utilized in the polymerization of other olefins, such as propylene-based polymers including any of the additional ot-olefins described herein above. Exemplary ethylene-based polymers include homopolymers and copolymers of ethylene and an additional ot-olefin. The ethylene-based polymers may also be interpolymers comprising ethylene and more than one additional a-olefin. 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).

[0074] In embodiments, the ethylene-based polymer produced by the methods described herein may comprise at least 50 weight percent (wt%) units derived from ethylene, at least 60 wt% units derived from ethylene, at least 70 wt% units derived from ethylene, at least 80 wt% units derived from ethylene, at least 90 wt% units derived from ethylene, at least 95 wt% units derived from ethylene, at least 98 wt% units derived from ethylene, at least 9986265-WO-PCT / DOW 86265 WO22wt% units derived from ethylene, at least 99.5 wt% units derived from ethylene, or at least 99.9 wt% units derived from ethylene.

[0075] In some embodiments, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a weight average molecular weight from 1,000 g / mol to 500,000 g / mol, from 1,000 g / mol to 400,000 g / mol, from 1,000 g / mol to 300,000 g / mol, from 1,000 g / mol to 250,000 g / mol, from 1,000 g / mol to 200,000 g / mol, from 2,000 g / mol to 200,000 g / mol, from 4,000 g / mol to 200,000 g / mol, or from 4,000 g / mol to 175,000 g / mol.

[0076] In some embodiments, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has 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 embodiments, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI from 1 to 50. In other embodiments, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI from 1 to 20. In some embodiments, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI from 1 to 15. In some embodiments, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI from 1 to 10, from 1 to 5, from 1 to 3, from 1 to 2.5, or from 1.5 to 2.5. In some embodiments, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI less than 2.

[0077] In embodiments, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a melt temperature of at least 100 °C, at least 110 °C, at least 115 °C, at least 120 °C, at least 122 °C, at least 124 °C, at least 126 °C, at least 128 °C, or at least 130 °C. In embodiments, the ethylene-based polymer has a melt temperature of from 124 °C to 132 °C.

[0078] 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, which86265-WO-PCT / DOW 86265 WO23may 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)?, 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.

[0079] 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.

[0080] Measurement Standards

[0081] HT-GPC Analysis with IR Detection of Octene Incorporation

[0082] 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. Decane (10 pL) is added to each sample for use as an internal flow marker. Samples are first diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm of butylated hydroxytoluene (BHT) to a concentration of 10 mg / mL and dissolved by stirring at 160 °C for 120 minutes. Prior to injection, samples are further diluted with TCB stabilized with BHT to a concentration of 2 mg / mL. Samples (250 pL) are eluted through one PL-gel 20 pm (50 x 7.5 mm) guard column followed by two PL-gel 20 pm (300 x 7.5 mm) Mixed-A columns maintained at 160 °C with TCB stabilized with BHT at a flow rate 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 3rd-order MW calibration curve with apparent units adjusted to homo-polyethylene (PE) using known Mark-Houwink coefficients for PS and PE. Octene incorporation is determined by use of a linear calibration developed by analyzing copolymers of known compositions.

[0083] Melt Temperature

[0084] Melt temperature is determined via Differential Scanning Calorimetry according to ASTM D3418-08, which is incorporated herein by reference in its entirety. About 5 to 8 mg of sample is weighed and placed in a DSC pan. The lid is crimped on the pan to ensure a closed atmosphere. The sample pan is placed in a DSC cell, and then heated, at a rate of86265-WO-PCT / DOW 86265 WO24approximately 10°C / min, to a temperature of 180°C for PE (230°C for PP). The sample is kept at this temperature for three minutes. Then, the sample is cooled at a rate of 10°C / min to -90°C for PE (-60°C for PP), and kept isothermally at that temperature for three minutes. The sample is next heated at a rate of 10°C / min, until complete melting (second heat). Unless otherwise stated, melting point (Tm) and the glass transition temperature (Tg) of each polymer are determined from the second heat curve, and the crystallization temperature (Tc) is determined from the first cooling curve. The respective peak temperatures for the Tmand the Tcare recorded. The percent crystallinity can be calculated by dividing the heat of fusion (Hf), determined from the second heat curve, by a theoretical heat of fusion of 292 J / g for PE (165 J / g for PP), and multiplying this quantity by 100 (for example, % cryst. = (Hf / 292 J / g) x 100 (for PE)).

[0085] One or more features of the present disclosure are illustrated in view of the examples as follows:EXAMPLES

[0086] All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted.

[0087] 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.

[0088] Examples 1 to 3 are synthetic procedures for three inventive metal-ligand complexes of the present disclosure (MLC-A to MLC-C). Example 4 describes polymerization results obtained using the metal-ligand complexes prepared according to Examples 1 to 3. It should be understood that Examples 1-4 are provided to illustrate embodiments described in this disclosure and are not intended to limit the scope of this disclosure or its appended claims.

[0089] Synthesis of Inventive Metal-Ligand Complexes86265-WO-PCT / DOW 86265 WO25Example 1MLC-Ai) n-BuLi ii) ScCI3iii) LiCH2SiMe3Et2O / toluene

[0090] ft-Butyl lithium (2.7 mol / L, 0.531 mL, 1.44 mmol) in hexanes was added to a room temperature (22-23 °C suspension of 2,7-ditert-butyl-9-[cyclopenta-l,3-dien-l-yl(diphenyl)methyl]-9H-fluorene (0.350 g, 0.688 mmol) in Et? O (8 mL) and toluene (2 mL). The mixture turned yellow, then orange, and finally a deep red / orange after 22 hours. A slurry of tri chloroscandium (0.109 g, 0.722 mmol) in Et? O (4 mL) was added at room temperature, then the mixture was stirred overnight at room temperature. The temperature was increased to 33 °C, and the reaction was held at this temperature for 40 h. THF (150 uL) was added, and the mixture was strirred at 33 °C for 54 hours. The reaction was divided in half, then to one half was added (trimethylsilyl)methyllithium (1.0 mol / L in pentane, 0.310 mL, 0.310 mmol), and the mixture was stirred at room temperature for 18 hours. The mixture turned from red / orange to yellow / brown.

[0091] After this time the solvent was removed under reduced pressure. Pentane (10 mL) was added to the concentrate which was then passed through a CELITE pad. The orange solution began to turn red / orange. The pad was washed with additional pentane (10 mL). The combined pentane extracts were concentrated to dryness then evaporated from pentane (3 x 3 mL). Pentane (8 mL) was added and an insoluble orange / yellow solid formed. The mixture was placed in a freezer (-33 °C) for two days, then the orange pentane layer was removed by pipet to leave behind ayellow / orange solid (179 mg). Based upon splitting up of the reactions the theoretical yield was 244 mg. Overall yield was 73%.

[0092] *H NMR (400 MHz, Benzene-d6) 8 8.22 (d, J = 7.8 Hz, 1H), 8.08 (d, J = 8.0 Hz, 1H), 7.98 (d, J = 8.7 Hz, 1H), 7.41 (dd, J = 9.0, 1.6 Hz, 1H), 7.16 (t, J = 7.6 Hz, 1H), 7.11 (d, J = 7.2 Hz, 1H), 7.00 (td, J = 7.6, 1.6 Hz, 2H), 6.95 - 6.84 (m, 3H), 6.74 (dd, J = 8.7, 1.7 Hz, 1H), 6.61 (d, J = 16.8 Hz, 2H), 5.98 (d, J = 3.0 Hz, 1H), 5.74 (d, J = 2.7 Hz, 1H), 5.65 (s,86265-WO-PCT / DOW 86265 WO261H), 2.84 (d, J = 6.9 Hz, 2H), 2.53 (d, J = 6.9 Hz, 2H), 1.16 (s, 9H), 0.99 (s, 9H), 0.80 (d, J = 4.7 Hz, 4H), -0.00 (s, 9H), -1.72 (d, J = 12.5 Hz, 1H), -2.96 (d, J = 12.5 Hz, 1H).Example 2MLC-B

[0093] In a glovebox, a 20 mL vial was charged with Ligand B (0.244 g, 0.378 mmol, 1.00 equiv) and 5.5 mL dry diethyl ether. Ligand B was prepared according to the procedure described in Japanese Publication No. 2008-231266 A. The mixture was stirred and treated with n-butyl lithium (2.5 M in hexane, 0.318 mL, 0.794 mmol, 2.10 equiv). The mixture stirred overnight.

[0094] Solvent was removed by vacuum pump, and the red solid residue was treated with 5 mL toluene. ScC13-3THF (0.146 g, 0.397 mmol, 1.05 equiv) was added to the mixture. After two hours, a small aliquot was removed and diluted in CeDe for Proton NMR analysis, which indicated the presence of the Sc-Cl complex Inventive B-Cl.

[0095] A solution of LiCH2SiMe3 (1.0 M in pentane, 0.378 mL, 0.378 mmol, 1.00 equiv) was injected into the solution. Stirring continued overnight.

[0096] The red, heterogeneous solution was concentrated to remove solvent. The residue was suspended in ~6 mL dry dichloromethane. The slurry was filtered through a 0.45 um syringe filter. The filtrate was concentrated to a red residue. The solid was dissolved in 5 mL pentane then was concentrated to dryness. The pentane wash / evaporation cycle was repeated two more times. The solid was dissolved in 1 mL pentane, and was chilled in a glovebox freezer overnight.

[0097] A pale red (almost white) solid precipitated. The red liquid was removed by decantation. The solid was rinsed with two small (<1 mL) portions of pentane. The solid was dried under vacuum and the pentane liquid phase was concentrated to dryness (33 mg, 10%). Proton NMR indicated that the THF ligand was labile and the product was a mixture of the complex with and without THF coordinated.86265-WO-PCT / DOW 86265 WO27

[0098] *H NMR (500 MHz, CD2CI2) 58.07 - 7.78 (m, 4H), 7.69 - 7.53 (m, 2H), 7.31 -7.10 (m, 3H), 7.09 - 6.96 (m, 2H), 6.62 - 6.42 (m, 2H), 6.21 (s, 1H), 5.74 - 5.66 (m, 2H), 3.81 - 2.93 (m, 4H), 2.37 - 2.27 (m, 6H), 1.74 - 1.55 (m, 10H), 1.50 - 1.31 (m, 14H), 1.08 - 0.91 (m, 12H), -0.33 (s, 9H), -1.97 (d, J = 12.5 Hz, 1H), -3.17 (d, J = 12.6 Hz, 1H).Example 3MLC-Cn-BuLi then ScClj-STHF MeLi Et2O / toluene toluene, rtInventive C-Cl MLC-C

[0099] In a glovebox, a 40 mL vial was charged with Ligand C (0.354 g, 0.756 mmol, 1.00 equiv), 8.8 mL diethyl ether, and 2.2 mL toluene. Ligand C was prepared according to the procedure described in U. S. Patent No. 10,934,375 B2. The mixture was stirred vigorously and was treated with n-butyl lithium (2.5 M in hexane, 0.636 mL, 1.59 mmol, 2.10 equiv). The mixture was stirred for 3 hours and gradually turned chalky yellow. ScC13-3THF (0.292 g, 0.794 mmol, 1.05 equiv) was added to the mixture and stirring continued for 14 hours. Crude NMR of the complex Inventive C-Cl showed that more of the rac isomer had formed. The slurry was concentrated to dryness and suspended in ~10 mL dichloromethane. The slurry was filtered through a 0.45 um syringe filter to remove solids. The filtrate was concentrated to give a yellow-orange solid.

[0100] In a glovebox, a 20 mL vial was charged with the Inventive C-Cl complex (0.188 g, 0.304 mmol, 1.00 equiv) and 6 mL dry toluene. The mixture was treated with MeLi (2.77 M in diethoxymethane, 98.6 uL, 0.9 equiv). The mixture stirred for 2 hours. Solvent was removed by vacuum pump. The residue was suspended in ~4 mL toluene and filtered through a 0.45 um syringe filter. The filtrate was concentrated. The yellow residue was suspended in ~4 mL pentane and was concentrated to dryness. The pentane wash / evaporation cycle was repeated two more times. The residue was dissolved in ~1 mL dry toluene and ~4 mL pentane was layered on top. The material was chilled in the glovebox freezer overnight.

[0101] The yellow solid was removed by filtration and was washed with a small portion of pentane. The solid was dried under vacuum. 43.4 mg of solid was isolated (24%).86265-WO-PCT / DOW 86265 WO28

[0102] *H NMR (400 MHz, C6D6) 58.00 (d, J = 8.4 Hz, 1H), 7.87 (d, J = 8.6 Hz, 1H), 7.71 (ddd, J = 8.1, 3.3, 1.4 Hz, 4H), 7.33 (d, J = 6.9 Hz, 1H), 7.27 - 7.17 (m, 6H), 7.12 - 7.06 (m, 2H), 6.88 (d, J = 6.9 Hz, 1H), 6.80 (dd, J = 8.5, 7.0 Hz, 1H), 6.14 (s, 1H), 2.68 (q, J = 7.1 Hz, 2H), 2.46 (dq, J = 8.1, 4.3 Hz, 2H), 2.37 (s, 3H), 2.29 (s, 3H), 1.20 (d, J = 3.4 Hz, 3H), 1.10 (s, 3H), 0.78 - 0.63 (m, 4H), -0.89 (s, 3H).

[0103] 13C NMR (101 MHz, C6D6) 5 142.72, 141.49, 137.03, 136.65, 134.74, 131.96, 131.81, 130.34, 130.16, 129.42, 128.98, 128.69, 128.42, 128.13, 128.11, 126.99, 126.46, 124.37, 124.25, 122.31, 122.16, 120.84, 119.80, 114.24, 109.66, 94.56, 94.29, 70.64, 23.83, 18.68, 18.14, 3.01, 2.52.

[0104] The structures of the inventive metal-ligand complexes MLC-A, MLC-B, and MLC-C are shown below along with structures of comparative metal-ligand complexes CMLC-A, CMLC-B, and CMLC-C:MLC-BCMLC-A CMLC-B CMLC-C Example 4Polymerization Reactions

[0105] Batch Reactor Polymerization Procedure

[0106] Procedure 1: Raw materials (ethylene, 1 -octene) and the process solvent (a narrow boiling range high-purity isoparaffinic solvent trademarked ISOPAR E commercially available from ExxonMobil Corporation) are purified with molecular sieves before86265-WO-PCT / DOW 86265 WO29introduction into the reaction environment. A one gallon (3.79 L) stirred autoclave reactor is charged with ISOPAR E, and 1 -octene. The reactor is then heated to the desired temperature and charged with ethylene to reach the desired pressure. Hydrogen is also added at this point if desired. The catalyst composition is prepared in a drybox under inert atmosphere by mixing the desired pro-catalyst and optionally one or more addtives as desired, with additional solvent to give a total volume of about 15-20 mL. The activated catalyst mixture is then quick-injected into the reactor. The reactor pressure and temperature are kept constant by feeding ethylene during the polymerization and cooling the reactor as needed. After 10 minutes, the ethylene feed is shut off and the solution transferred into a nitrogen-purged resin kettle. The polymer was thoroughly dried in a vacuum oven, and the reactor is thoroughly rinsed with hot ISOPAR E between polymerization runs.

[0107] Procedure 2: The batch reactor polymerizations are 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, prefilled with a catalyst-kill solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). The dump pot is vented to a 30 gallon blow-down tank, with both the pot and the tank purged with nitrogen.

[0108] 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 are passed through two columns, the first containing activated A2 alumina, the second containing activated Q5. The ethylene is passed through two columns, the first containing activated A204 alumina and activated 4A mol sieves, the second containing Q5 reactant. The N2, used for transfers, is passed through a single column containing A204 alumna, 4 A mol sieves, and Q5.

[0109] 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 using a differential pressure method. After liquid feed addition, the reactor is heated up to the polymerization temperature set point. Ethylene is added to the reactor when at reaction86265-WO-PCT / DOW 86265 WO30temperature to maintain reaction pressure set point. Ethylene addition amounts are monitored by a micro-motion flow meter.

[0110] The catalyst and co-catalyst components are mixed with the appropriate amount of purified toluene to achieve a solution of desired molarity. The catalyst and co-catalyst components are handled in an inert glove box, drawn into a syringe and pressure transferred into the catalyst shot tank. This is followed by three rinses of toluene, 5 mL each. Immediately after catalyst addition the run timer begins. If ethylene is used, it is then added by the Camile to maintain reaction the pressure set point in the reactor. These polymerizations are run for 10 minutes, then the agitator is stopped, and the bottom dump valve is opened to empty the reactor contents into the dump pot. The dump pot contents are poured into trays placed in a lab hood where the solvent is evaporated off overnight. The trays containing the remaining polymer are then transferred to a vacuum oven, where they are heated at 140 °C under vacuum to remove any remaining solvent. After the trays cool to ambient temperature, the polymers are weighed for yield / efficiencies, and submitted for polymer testing.

[0111] Tables 1-3 present results of ethylene / 1 -octene copolymerization reactions for MLC-A to MLC-C and CMLC-A to CMLC-C, following the Batch Reactor Polymerization Procedure disclosed herein. Polymerization experiments were performed at polymerization temperatures of 140 °C, 160 °C, and 190 °C, and for each run, the catalyst efficiency and resulting polymer properties in terms of the melting temperature, polydispersity index (PDI), weight average molecular weight, and octene incorporation were determined and are reported in Tables 1-3.TABLE 1: Batch reactor polymerization results for MLC-A and CMLC-A at 160 °C Reaction Efficiency Metal-Ligand HC Temp2TmMw PDI C8 omplex (°C) (pmol) (g poly / g (°C) (g / mol) (Mw / M„) (wt%)metal)MLC-A1160 0 589,000 129.8 31,680 2.22 ND MLC 40-A1160 730,000 128.4 10,251 2.18 ND0 CMLC-A2160 224,000 82.1 210,785 2.12 20 CMLC-A2160 40 210,000 86.6 2.14 21 78,057Polymerization conditions: Procedure 1: 1,250 g Isopar E; 60 g octene; ethylene pressure = 410 psi1MMAO-7:active metal = 20:186265-WO-PCT / DOW 86265 WO312precataly st: activator = 1:1.2; activator = [HNMe(C₁₈H₃₇)₂][B(C₆F₅)₄]; BHT-TEA: active metal = 50:1ND = below detection limit (<2.00 wt%)TABLE 2: Batch reactor polymerization results for MLC-A and CMLC-A at 190 °C Reaction Efficiency Metal-Ligand HTemp2TmMw PDI C8 Complex (pmol) (g poly / g (°C (g / mol) (Mw / M„) (wt%)(°C) metal) )MLC-A1190 0 258,000 126.8 7,007 2.16 ND 40 MLC-A1190 570,000 4,030 ND 124.9 1.890 CMLC-A2190 344,000 108,332 2.23 15 94.9CMLC-A2190 40 436,000 2.42 16 97.7 49,827Polymerization conditions: Procedure 1: 1,250 g Isopar E; 65 g octene; ethylene pressure = 410 psi1MMAO-7:active metal = 20:12precataly st: activator = 1:1.2; activator = [HNMe(C₁₈H₃₇)₂][B(C₆F₅)₄]; BHT-TEA: active metal = 50:1ND = below detection limit (<2.00 wt%)TABLE 3: Batch reactor polymerization results for MLC-B, CMLC-B, MLC-C, and CMLC-C at 140 °C and 190 °CReaction Catalyst Efficiency Metal-Ligand TmPDI C8 Mw Temp Loading (g poly / g (g / mol) (wt%) (Mw / M„) Complex (°C) metal) (^.mol) (°C)MLC-B 140 0.075 1,335,000 131.5 168,360 2.2 ND MLC-B 190 0.300 2,002,000 129.8 10,904 2.5 ND CMLC-B* 140 0.075 3,449,000 116.6 2.2 4.51 157,627MLC-C 140 0.065 5,510,000 NA 63,806 ND 2.7MLC-C 190 0.130 496,000 NA 7,212 ND 4.9CMLC-C 140 0.100 734,000 117.0 140,648 2.6 9.74 CMLC-C 190 0.300 194,000 108.4 24,520 5.8 11.01Polymerization conditions: Procedure 2: 43 g ethylene; ethylene pressure = 340 psi; 28 g octene; 500 g Isopar E; 10 umol MMA0-3A. Precatalyst: activator = 1:1.2; activator = [HNMe(C₁₈H₃₇)₂][B(C₆F₅)₄] for comparative examples only.* Run was conducted for 0.4 min and then stopped early due to 21 °C exothermMMAO-7: active metal = 20:1ND = below detection limit (<2.00 wt%)NA = not measured86265-WO-PCT / DOW 86265 WO32

[0112] As can be seen from Tables 1-3, the copolymerization reactions using catalyst systems including one of MLC-A, MLC-B, or MLC-C, each having a structure according to Formula (I), demonstrated good efficiency (greater than 200,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex) while also achieving high ethylene selectivity (greater than 98.0 wt% units derived from ethylene), at polymerization temperatures greater than or equal to 140 °C, and even at a polymerization temperature of 190 °C. In contrast, CMLC-A, CMLC-B, and CMLC-C, having identical structures as MLC-A, MLC-B, and MLC-C, respectively, but having a hafnium (CMLC-A) or zirconium (CMLC-B and CMLC-C) as the metal center, were unable to achieve a combination of high catalyst activity and high ethylene selectivity as demonstrated for MLC-A, MLC-B, and MLC-C. Accordingly, the catalyst systems and polymerization methods described herein using ansa-metallocene metal-ligand complexes having a structure according to Formula (I) show promise as ethylene-selective catalysts in multicatalyst systems.

[0113] 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.

[0114] 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.86265-WO-PCT / DOW 86265 WO33

[0115] 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.”

[0116] 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.

[0117] It should be understood that any two quantitative values assigned to a property or measurement may constitute a range of that property or measurement, and all combinations of ranges formed from all stated quantitative values of a given property or measurement are contemplated in this disclosure.

[0118] 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

1. 86265-WO-PCT / DOW 86265 WO2.343.CLAIMS1. A method of making an ethylene-based polymer, the method comprising:5.polymerizing, in a polymerization reactor, ethylene, or a combination of ethylene and at least one ot-olefin, in the presence of a catalyst system comprising a metal-ligand complex according to Formula (I):

7. 9.where:10.M is scandium, yttrium, or a lanthanide metal having an oxidation state of +3;11.X is a monodentate or bidentate ligand independently selected from unsaturated (C2–C30)hydrocarbon, unsaturated (C2–C30)heterohydrocarbon, (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, -N(RX)2, and -(CH2)wSi(Rx)3, where w is from 1 to 10, each Rxis independently selected from (Ci-C3o)hydrocarbyl and (Ci-C3o)heterohydrocarbyl, and optionally two or more Rxgroups are covalently linked;12.T is a Lewis base, wherein X and T are optionally covalently linked;13.each of R1-8is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H, wherein:14.optionally, R1and R2are covalently linked to form a ring;15.optionally, R3and R4are covalently linked to form a ring;16.optionally, R5and R6are covalently linked to form a ring;17.optionally, R7and R8are covalently linked to form a ring;18.R9and R10are independently selected from (Ci-C3o)hydrocarbyl and (Ci-C3o)heterohydrocarbyl; and19.W is carbon, silicon, or germanium. 86265-WO-PCT / DOW 86265 WO20.

352. The method of claim 1, wherein the Lewis base is (Ci-C2o)heterohydrocarbon comprising at least one oxygen heteroatom.

3. The method of claim 1, wherein T is tetrahydro furan, diethyl ether, or methyl tert-butyl ether (MTBE).

4. The method of any one of the preceding claims, wherein X is (Ci-Cio)alkyl or -CH2Si[(Ci-C2o)alkyl].

5. The method of any one of the preceding claims, wherein R9and R10are independently (Ci-C2o)hydrocarbyl.

6. The method of any one of the preceding claims, wherein R9and R10are independently substituted phenyl.

7. The method of any one of the preceding claims, wherein R4and R8are independently (Ci-Cio)alkyl.

8. The method of any one of the preceding claims, wherein R1and R2are covalently linked to form an aromatic ring, and wherein the metal-ligand complex has a structure according to Formula (la):28.(la)30. 32.where:33.M, X, T, W, and R3 10are defined as in Formula (I); and 86265-WO-PCT / DOW 86265 WO34.3635.each of R11-14is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H, wherein R12and R13are optionally covalently linked to form a ring.

9. The method of claim 8, wherein R3and R4are covalently linked to form an aromatic ring, and wherein the metal-ligand complex has a structure according to Formula (lb):

38. 40.where:41.M, X, T, W, and R5-14are defined as in Formula (la); and42.each of R15-18is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H, wherein R16and R17are optionally covalently linked to form a ring.

10. The method of claim 9, wherein:44.R12and R13are covalently linked to form a non-aromatic ring; and45.R16and R17are covalently linked to form a non-aromatic ring.

11. The method of claim 9, wherein:47.at least one of R11-14is (C4-Cio)alkyl; and48.at least one of R15-18is (C4-Cio)alkyl. 86265-WO-PCT / DOW 86265 WO49.3712. The method of claim 8, wherein R5and R6are covalently linked to form an aromatic ring, and wherein the metal-ligand complex has a structure according to Formula (Ic):

52. 54.where:55.M, X, T, W, R3, R4, and R7-14are defined as in Formula (la); and56.each of R19-22is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H.

13. The method of claim 12, wherein:58.at least one of R11-14is (Ce-C2o)aryl; and59.at least one of R19-22is (Ce-C2o)aryl.

14. The method of any one of the preceding claims, wherein M is scandium.86265-WO-PCT / DOW 86265 WO61.3815. The method of any one of claims 1-8, wherein the metal-ligand complex is selected from MLC-A, MLC-B, or MLC-C:

64.

65. MLC-C16. The method of any one of the preceding claims, wherein the polymerizing is performed at a polymerization temperature of at least 140 °C.

17. The method of any one of the preceding claims, wherein the polymerizing produces at least 200,000 grams of ethylene-based polymer per gram metal of the metal-ligand complex.

18. The method of any one of the preceding claims, wherein the ethylene-based polymer comprises at least 98 wt% units derived from ethylene.

19. The method of any one of the preceding claims, wherein the method comprises polymerizing, in the polymerization reactor, the combination of ethylene and the at least one ot-olefin.86265-WO-PCT / DOW 86265 WO70.3920. A catalyst system comprising a metal-ligand complex according to Formula (II):

73. 75.where:76.X is a monodentate or bidentate ligand independently selected from unsaturated (C2–C30)hydrocarbon, unsaturated (C2–C30)heterohydrocarbon, (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, -N(RX)2, and -(CH2)wSi(Rx)3, where w is from 1 to 10, each Rxis independently selected from (Ci-C3o)hydrocarbyl and (Ci-C3o)heterohydrocarbyl, and optionally two or more Rxgroups are covalently linked;77.T is a Lewis base, wherein X and T are optionally covalently linked;78.each of R1-8is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H, wherein:79.optionally, R1and R2are covalently linked to form a ring;80.optionally, R3and R4are covalently linked to form a ring;81.optionally, R5and R6are covalently linked to form a ring;82.optionally, R7and R8are covalently linked to form a ring;83.R9and R10are independently selected from (Ci-C3o)hydrocarbyl and (Ci-C3o)heterohydrocarbyl; and84.W is carbon, silicon, or germanium.

21. The catalyst system of claim 20, wherein the Lewis base is (Ci-C2o)heterohydrocarbon comprising at least one oxygen heteroatom.86265-WO-PCT / DOW 86265 WO86.4022. The catalyst system of claim 20, wherein T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

23. The catalyst system of any one of claims 20-22, wherein X is (Ci-Cio)alkyl or -CH2Si[(Ci-C2o)alkyl].

24. The catalyst system of any one of claims 20-23, wherein R9and R10are independently (Ci-C2o)hydrocarbyl.

25. The catalyst system of any one of claims 20-24, wherein R9and R10are independently substituted phenyl.

26. The catalyst system of any one of claims 20-25, wherein R4and R8are independently (Ci-Cio)alkyl.

27. The catalyst system of any one of claims 20-26, wherein R1and R2are covalently linked to form an aromatic ring, and wherein the metal-ligand complex has a structure according to Formula (Ila):

94.

95. R696.where:97.X, T, W, and R3-10are defined as in Formula (II); and98.each of R11-14is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H, wherein R12and R13are optionally covalently linked to form a ring. 86265-WO-PCT / DOW 86265 WO99.4128. The catalyst system of claim 27, wherein R3and R4are covalently linked to form an aromatic ring, and wherein the metal-ligand complex has a structure according to Formula (lib):

102. 104.where:105.X, T, W, and R5-14are defined as in Formula (Ila); and106.each of R15-18is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H, wherein optionally, R16and R17are optionally covalently linked to form a ring.

29. The catalyst system of claim 28, wherein:108.R12and R13are covalently linked to form a non-aromatic ring; and109.R16and R17are covalently linked to form a non-aromatic ring.

30. The catalyst system of claim 28, wherein:111.at least one of R11-14is (C4-Cio)alkyl; and112.at least one of R15-18is (C4-Cio)alkyl. 86265-WO-PCT / DOW 86265 WO113.4231. The catalyst system of claim 27, wherein R5and R6are covalently linked to form an aromatic ring, and wherein the metal-ligand complex has a structure according to Formula (lie):115.(lie)117. 119.where:120.X, T, W, R3, R4, and R7-14are defined as in Formula (Ila); and121.each of R19-22is independently selected from (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, halogen, and -H.

32. The catalyst system of claim 31, wherein:123.at least one of R11-14is (Ce-C2o)aryl; and124.at least one of R19-22is (Ce-C2o)aryl.

33. The method of any one of claims 20-27, wherein the metal-ligand complex is selected from MLC-A, MLC-B, or MLC-C:

127.

128. MLC-A MLC-B 86265-WO-PCT / DOW 86265 WO129.43130. 132.MLC-C

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