Cyclopentadienyl-phenoxy complexes for olefin polymerization

Abstract

Catalyst systems comprising a metal-ligand complex having a structure according to Formula (I): where M is a metal chosen from scandium or yttrium; X is chosen from silicon or germanium; L is a monodentate or bidentate ligand selected from the group consisting of (C1−C30) hydrocarbyl, (C1−C30) heterohydrocarbyl, (C6−C30)aryl, (C3−C30) heteroaryl, halogen and –H; and Z is a Lewis base. R1, R2, R3, and R4 are 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; R5, R6, R7, and R8 are 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; R9 and R10 are 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; 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

86264-WO-PCT / DOW 86264 WO1CYCLOPENT ADIENYL-PHENOXY COMPLEXES FOR OLEFIN POLYMERIZATIONCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 736,073 filed December 19, 2024, the contents of which are incorporated in their entirety herein.TECHNICAL FIELD

[0002] The present disclosure generally relates to catalyst systems and processes that may be utilized for olefin polymerization, and, more specifically, to catalyst systems involving cyclopentadienyl-phenoxy complexes and to olefin polymerization processes incorporating such catalyst systems.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 polyethylene polymerization process can be varied in a number of respects to produce a wide variety of resultant polyethylene resins having different physical properties that render the various resins suitable for use in different applications. The ethylene monomers and, optionally, one or more co-monomers are present in liquid diluents (such as solvents), such as an alkane or isoalkane, such as isoparaffin liquids (i.e., Isopar-E). Hydrogen may also be added to the reactor. The reactants in the diluent 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 the polyethylene 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 polyethylene product from the diluent and the unreacted reactants, with the diluent and unreacted reactants typically being recycled back into the reactor.86264-WO-PCT / DOW 86264 WO2Alternatively, the reaction mixture may be sent to a second reactor, serially connected to the first reactor, where a second polyethylene fraction may be produced. Despite the research efforts in developing catalyst systems suitable for olefin polymerization, such as polyethylene polymerization, there is still a need to increase the efficiencies of catalyst systems that are capable of producing polymer with high ethylene selectivity and a range of molecular weight capabilities.SUMMARY

[0005] Catalyst systems disclosed herein include a metal-ligand complex having a structure according to Formula (I):

[0006] In Formula (I), M is a metal chosen from scandium or yttrium, and X is chosen from silicon or germanium.

[0007] R1, R2, R3, and R4may be independently selected from the group consisting of(Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H, where each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl, (C3-C3o)heteroaryl, and -H. R1and R2may be optionally covalently linked to form an aromatic ring or a non-aromatic ring.

[0008] R5, R6, R7, and R8may be independently selected from the group consisting of(Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H, where each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl, (C3-C3o)heteroaryl, and -H.86264-WO-PCT / DOW 86264 WO3

[0009] R9and R10are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl, (C3“C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H, where each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl, (C3-C3o)heteroaryl, and -H.

[0010] In Formula (I) L may be selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl, (C3-C3o)heteroaryl, halogen and -H. Z may be a Lewis Base.

[0011] Polymerization processes, particularly methods of making ethylene-based polymers, include polymerizing ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of the catalyst system including a metal-ligand complex having a structure according to Formula (I), wherein the polymerizing comprises solution polymerization.DETAILED DESCRIPTION

[0012] Catalyst systems will now be described. It should be understood that the catalyst systems of this disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure. Rather, embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0013] Common abbreviations are listed below:

[0014] R, M, X, L, and Z: as defined above; Me : methyl; Et : ethyl; Ph : phenyl; Bn: benzyl; Mes: mesityl (2,4,6-trimethylphenyl); z-Pr : z o-propyl; zz-Bu : n-butyl; zz-BuLi : zz-butyllithium; t-Bu : tert-butyl; / -Oct : tert-octyl (2,4,4-trimethylpentan-2-yl); Tf : trifluoromethane sulfonate; : Et2O : diethyl ether; EtOH : ethanol; DCM or CH2CI2 : dichloromethane; DME : dimethoxyethane; DIW : deionized water; CeDe : deuterated benzene or benzene-c / 6 : CDCh : deuterated chloroform; THF : tetrahydrofuran; NEt3 : trimethylamine; TiCh : titanium tetrachloride; ScC13(THF)3 : Scandium chloride tetrahydrofuran complex; LiCEhSiMes : (trimethylsilyl)methyllithium; CpMe4 : 6 — tetramethylcyclopentadienyllithium; Na2SO4 : sodium sulfate; MgSO4 : magnesium sulfate; HC1 : hydrogen chloride; NaHCCh : sodium bicarbonate; NH4CI : ammonium chloride; N2 : nitrogen gas; PhMe: toluene; PPR : parallel pressure reactor; MAO : methylaluminoxane; MMAO : modified methylaluminoxane; GC : gas86264-WO-PCT / DOW 86264 WO4 chromatography; LC : liquid chromatography; RIBS-2: bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-) amine; NMR : nuclear magnetic resonance; MS: mass spectrometry; mmol : millimoles; mL : milliliters; M : molar; min or mins: minutes; h or hrs : hours; d: days; rpm: revolution per minute.

[0015] 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.

[0016] 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 terms “co-catalyst” and “activator” are interchangeable terms.

[0017] 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 atomcontaining 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.

[0018] 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 hydrogen86264-WO-PCT / DOW 86264 WO5 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.

[0019] 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.

[0020] In this disclosure, a (Ci-C3o)hydrocarbyl may be an unsubstituted or substituted (Ci-C3o)alkyl, (C3-C3o)cycloalkyl, (C3-Ci5)cycloalkyl-(Ci-Ci5)alkylene, (Ce-C3o)aryl, or (C6-Ci5)aryl-(Ci-Ci5)alkylene (such as benzyl (-CH2-C6H5)).

[0021] 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-C3o)alkyl are substituted (Ci-C2o)alkyl (such as benzyl (-CH2-C6H5)), substituted (Ci-Cio)alkyl, trifluoromethyl, and [C3s]alkyl. The term “[Cssjalkyl” means there is a maximum of 35 carbon atoms in the radical, including substituents, and is, for example, a (Ci5-C3o)alkyl substituted by one Rs, which is a (Ci-C5)alkyl, respectively. Each (Ci-C5)alkyl may be methyl, ethyl, 1 -propyl, 1 -methylethyl, 1,1 -dimethylethyl, or tert-butyl.

[0022] 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 aromatic86264-WO-PCT / DOW 86264 WO6 hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or non-fused and aromatic or nonaromatic. 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-Ci8)aryl; 2,4-bis([C2o]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9- one-l-yl.

[0023] The term “(C3-C3o)cycloalkyl” means a saturated cyclic hydrocarbon radical of from 3 to 30 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-C3o)cycloalkyl are unsubstituted (C3-C2o)cycloalkyl, unsubstituted (C3-Cio)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3-C3o)cycloalkyl are substituted (C3-C2o)cycloalkyl, substituted (C3-Cio)cycloalkyl, cyclopentanon-2-yl, and 1 -fluorocyclohexyl.

[0024] Examples of (Ci-C3o)hydrocarbylene include unsubstituted or substituted (C6-C3o)arylene, (C3-C3o)cycloalkylene, and (Ci-C3o)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.

[0025] The term “(Ci-C3o)alkylene” means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from 1 to 30 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-C3o)alkylene are unsubstituted86264-WO-PCT / DOW 86264 WO7(Ci-C2o)alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CEE)?-, -(CH2)e-, -(CH2)?-, -(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-C3o)alkylene 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-C3o)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.

[0026] The term “(C3-C3o)cycloalkylene” means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 30 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.

[0027] The term “heteroatom,” refers to an atom other than hydrogen or carbon. Examples of groups containing one or more than one heteroatom include O, S, S(O), S(O)2, Si(Rc)2, P(Rp), N(RN), - N=C(RC)2, -Ge(Rc)2“, or -Si(Rc)-, where each Rcand each Rpis unsubstituted (Ci-Ci8)hydrocarbyl or -H, and where each RNis unsubstituted (Ci-Ci8)hydrocarbyl. The term “heterohydrocarbon” refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. The term “(Ci-C3o)heterohydrocarbyl” means a heterohydrocarbon radical of from 1 to 30 carbon atoms, and the term“(Ci-C3o)heterohydrocarbylene” means a heterohydrocarbon diradical of from 1 to 30 carbon atoms. The heterohydrocarbon of the (Ci-C3o)heterohydrocarbyl or the(Ci-C3o)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-C3o)heterohydrocarbyl and (Ci-C3o)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), or86264-WO-PCT / DOW 86264 WO 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.

[0028] 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-Ci9)heterocycloalkyl-(Ci-C2o)alkylene, (C3-C2o)cycloalkyl-(Ci-Ci9)heteroalkylene, (C2-C i9)heterocy cloalkyl-(Ci-C2o)heteroalkylene, (Ci-C3o)heteroaryl, (Ci-Ci9)heteroaryl-(Ci-C2o)alkylene, (Ce-C2o)aryl- (Ci-Ci9)heteroalkylene, or (Ci-Ci9)heteroaryl-(Ci-C2o)heteroalkylene.

[0029] 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, (Ce-C2o)aryl- (Ci-Cio)heteroalkylene, or (Ci-C2o)heteroaryl-(Ci-Cio)heteroalkylene.

[0030] 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 may86264-WO-PCT / DOW 86264 WO9 be 1, 2, or 3; and each heteroatom may be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol- 1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-l-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1 ,2,4-triazol- 1-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 fused5.6-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 is1.7-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, 5,6-ring system is 9H-carbazol-9-yl. An Example of the fused 6, 6,6-ring system is acrydin-9-yl.

[0031] The term “(Ci-C3o)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-C3o)heteroalkylene” means a saturated straight or branched chain diradicals containing from 1 to 30 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.

[0032] Examples of unsubstituted (C2-C3o)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.

[0033] 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").

[0034] The term “saturated” means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorous, and86264-WO-PCT / DOW 86264 WO10 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 carbon-carbon double bonds, carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbonnitrogen, 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.

[0035] Catalyst systems herein include a metal-ligand complex having a structure according to Formula (I):

[0036] In Formula (I), M is a metal chosen from scandium or yttrium. X is chosen from silicon or germanium. L is a monodentate or bidentate ligand selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, halogen and -H.Z is a Lewis base. R1, R2, R3, and R4may be 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. R5, R6, R7, and R8are 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. R9and R10are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6-C3o)aryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H. In Formula (I), each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, and -H.

[0037] In some catalyst systems, M is scandium.

[0038] In Formula (I), L may bond with M through a covalent bond, a dative bond, or an ionic bond and may be a monodentate monoanionic ligand or a monodentate neutral ligand. In examples86264-WO-PCT / DOW 86264 WO11 in which L is a monodentate ligand, the monodentate ligand may be a neutral ligand or a monoanionic ligand. In examples in which L is a bidentate ligand, the bidentate ligand may be 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.

[0039] In example metal-ligand complexes in which L is a monodentate monoanionic ligand, the monoanionic ligand may be hydride, (Ci-C3o)hydrocarbyl carbanion, (Ci-C3o)heterohydrocarbyl carbanion, halide, nitrate, carbonate, phosphate, sulfate, HC(O)O , HC(O)N(H)’, (Ci-C2o)hydrocarbylC(0)0 . (Ci-C20)hydrocarbylC(O)N((Ci-C20)hydrocarbyl) ’, (Ci-C2o)hydrocarbylC(0)N(H)’, RKRLB) , RKRLN , RKO , 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 as defined above. In embodiments where L is a dianionic ligand, the dianionic ligand may be carbonate, oxalate (i.e., O2CC(O)O , (C2-C4o)hydrocarbylene dicarbanion, (Ci-C4o)heterohydrocarbylene dicarbanion, phosphate, or sulfate.

[0040] In example metal-ligand complexes in which L is a monodentate neutral ligand, the neutral ligand may be a neutral Lewis base group such as RJNRKRL, RKORL, RKSRL, or RJPRKRL, 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 as previously defined.

[0041] In example metal-ligand complexes, L may be -R'Si(Rc)3, each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6-C3o)aryl, (C3-C3o)heteroaryl, and -H, and R' is independently selected from the group consisting of (Ci-C3o)hydrocarbylene, and (Ci-C3o)heterohydrocarbylene. In specific example metal-ligand complexes, L may be chosen from -R'Si(Rc)3, wherein each Rcis independently selected from the group consisting of (Ci-C5)hydrocarbyl and (Ci-C5)heterohydrocarbyl, and R' is independently selected from the group consisting of (Ci-C5)hydrocarbylene and (Ci-C5)heterohydrocarbylene. L may be -CH2Si(CH3)3.

[0042] In example metal-ligand complexes, L 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.86264-WO-PCT / DOW 86264 WO12

[0043] In example metal-ligand complexes, L is (Ci-Cio)alkyl, -CH2Si[(Ci-C2o)alkyl], (C6-C2o)aryl, or a halogen. In some example metal-ligand complexes, L may be (Ci-Cio)alkyl or -CH2Si[(Ci-C2o)alkyl]. In some example metal-ligand complexes, L may be methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro. In specific example metal-ligand complexes, L may be methyl or trimethylsilyl methyl.

[0044] In Formula (I), Z 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 embodiments where L is bidentate, L and Z may be covalently linked.

[0045] In some example metal-ligand complexes, the Lewis base may be a hydrocarbon. An example of a neutral hydrocarbon includes, but is not limited to, 1,3 -butadiene. An example of anionic hydrocarbon includes, but is not limited to, cyclopentadiene.

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

[0047] In one or more example metal-ligand complexes, the Lewis base may be a monodentate neutral ligand. In specific example metal-ligand complexes, the neutral ligand is a neutral group such as 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 as previously defined.

[0048] In example metal-ligand complexes, R1, R2, R3, and R4may be independently a (Ci-C5)alkyl. In particular example metal-ligand complexes, R1, R2, R3, and R4are methyl.

[0049] In example metal-ligand complexes, R5, R6, R7, and R8may be independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ce-C3o)aryl, halogen, and -H. In particular example metal-ligand complexes, R5, R6, R7, and R8may be independently selected from the group consisting of (Ci-Cio)hydrocarbyl, halogen, and -H. In various example metal-ligand complexes, at least one of R5, R6, R7, or R8may be tert-butyl. In various example metal-ligand86264-WO-PCT / DOW 86264 WO13 complexes, R5and R7may be -H, R6and R8may be independently selected from (C1-C10- )hydrocarbyl, or both. In particular example metal-ligand complexes, R5and R7are -H, R6is methyl, and R8is tert-butyl.

[0050] R9and R10may be independently selected from the group consisting of (Ci-Cio)hydrocarbyl, (Ci-Cio)heterohydrocarbyl, (Ce-Ci2)aryl, (C3-Ci2)heteroaryl, -ORC, -Si(Rc)s, -Ge(Rc)3, halogen, and -H. In example metal-ligand complexes, R9and R10may be independently selected from (Ci-Cio)hydrocarbyl. R9and R10may be independent selected from the group consisting of methyl, ethyl propyl, and butyl. In specific example metal-ligand complexes, R9and R10are methyl.

[0051] In some example metal-ligand complexes, R1and R2may be covalently linked to form an aromatic ring or a non-aromatic ring. In some example metal-ligand complexes, R2and R3may be covalently linked to form an aromatic ring or a non-aromatic ring. In some example metalligand complexes, R3and R4may be covalently linked to form an aromatic ring or a non-aromatic ring.

[0052] In various example metal-ligand complexes wherein R1and R2are covalently linked to form an aromatic ring, the metal-ligand complex may have a structure according to Formula (II):

[0053] In Formula (II), R3, R4, R5, R6, R7, R8, R9, R10, X, L, Z, and M are defined as in Formula (I); and R11, R12, R13, and R14may be independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (Ce-C3o)aryl, (C3-C3o)heteroaryl, -ORC,86264-WO-PCT / DOW 86264 WO14-Si(Rc)s, -Ge(Rc)3, halogen, and -H. In formula (II), R11and R12may be covalently linked to form an aromatic ring or a non-aromatic ring. In formula (II), R12and R13may be covalently linked to form an aromatic ring or a non-aromatic ring. In formula (II), R13and R14may be covalently linked to form an aromatic ring or a non-aromatic ring.

[0054] In some example metal-ligand complexes, any or all of the chemical groups (e.g., L, Z, and R'-R10) of the metal-ligand complex of Formula (I) may be unsubstituted. In other example metal-ligand complexes, none, any, or all of the chemical groups L, Z, and R ' R '0of the metal-ligand complex of Formula (I) may be substituted with one or more than one Rs. When two or more than two Rsare bonded to a same chemical group of the metal-ligand complex of Formula (I), the individual Rsof the chemical group may be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some example metal-ligand complexes, none, any, or all of the chemical groups y, Z, and R'-R10may be persubstituted with Rs. In the chemical groups that are persubstituted with Rs, the individual Rsmay all be the same or may be independently chosen.

[0055] In some example metal-ligand complexes, any or all of the chemical groups (e.g., L, Z, and R4-R14) of the metal -ligand complex of Formula (II) may be unsubstituted. In other example metal-ligand complexes, none, any, or all of the chemical groups L, Z, and R4-R14of the metal-ligand complex of Formula (II) may be substituted with one or more than one Rs. When two or more than two Rsare bonded to a same chemical group of the metal-ligand complex of Formula (II), the individual Rsof the chemical group may be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, none, any, or all of the chemical groups L, Z, and R4-R14may be persubstituted with Rs. In the chemical groups that are persubstituted with Rs, the individual Rsmay all be the same or may be independently chosen.

[0056] In illustrative embodiments, the catalyst systems may include a metal-ligand complex according to Formula (I) having the structure of any of the metal-ligand complexes (MLC) 1-8 listed below:86264-WO-PCT / DOW 86264 WOMLC 7, MLC 8, or combinations thereof.86264-WO-PCT / DOW 86264 WO16

[0057] In particular embodiments, the metal-ligand complex may be any one of MLC 1, MLC 2, MLC 3, MLC 4, or combinations thereof.

[0058] Polymerization processes herein include polymerizing ethylene monomer, or a combination of ethylene monomer and at least one 1 -alkene comonomer, in the presence of a catalyst system comprising a metal-ligand complex according to Formula (I).

[0059] Additive Component

[0060] 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 metal-ligand complex. 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.

[0061] 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.

[0062] 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 methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.

[0063] 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,86264-WO-PCT / DOW 86264 WO17 tri((C6_Ci8)aryl)boron compounds, and halogenated (including perhalogenated) derivatives thereof.

[0064] 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 co-catalyst 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.

[0065] 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.

[0066] 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-Cis)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.

[0067] Polymerization Methods86264-WO-PCT / DOW 86264 WO18

[0068] Polymerization methods disclosed herein include polymerizing, in a polymerization reactor, ethylene and at least one a-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.

[0069] In particular embodiments the ethylene-based polymer may be produced via solution polymerization. In one polymerization method, the ethylene-based polymer may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and at least one a-olefin are polymerized in the presence of the catalyst system, as described herein, and optionally one or more co-catalyst 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 and at least one a-olefin are polymerized in the presence of the catalyst system, as described herein, in both reactors.

[0070] 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 and at least one a-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.

[0071] In some polymerization methods described herein, the at least one a-olefin may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary 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, the at least one a-olefin may be selected from the group consisting of propylene, 1 -butene, 1 -hexene, and 1 -octene. In some polymerization methods, the at least one a-olefin may be selected from the group consisting of 1 -hexene and 1 -octene. In specific polymerization methods, the at least one a-olefin comprises 1 -octene.86264-WO-PCT / DOW 86264 WO19

[0072] As discussed above and demonstrated through the examples submitted herewith, it has been unexpectedly found that the catalyst systems described herein comprising metal-ligand complexes of Formula (I) 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.

[0073] In some polymerization methods described herein, 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 (g poly / g metal). In 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 metal-ligand 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.

[0074] Polyolefins

[0075] The catalyst systems and polymerization methods described in the preceding paragraphs may be utilized to produce olefin-based polymers. Though 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. The ethylene-based polymers may also be interpolymers comprising ethylene and more than one additional ot-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).86264-WO-PCT / DOW 86264 WO20

[0076] As examples, 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 99 wt% units derived from ethylene, at least 99.5 wt% units derived from ethylene, or at least 99.9 wt% units derived from ethylene.

[0077] As further examples, 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.

[0078] As further examples, 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. As further examples, 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. As further examples, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI from 1 to 15. As further examples, 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. As further examples, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI less than 2.

[0079] As further examples, 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.

[0080] 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. The86264-WO-PCT / DOW 86264 WO21 ethylene-based polymers may compromise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the ethylene-based polymers and the one or more additives. The ethylene-based polymers may further comprise fdlers, which may include, but are not limited to, organic or inorganic fdlers. The ethylene-based polymers may contain from about 0 to about 20 weight percent fdlers such as, for example, calcium carbonate, talc, or Mg(OH)?, based on the combined weight of the ethylene-based polymers and all additives or fdlers. The ethylene-based polymers may further be blended with one or more polymers to form a blend.

[0081] 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.

[0082] The catalyst systems described in this disclosure yield unique polymer properties as a result of the high molecular weights of the polymers formed and the amount of the co-monomers incorporated into the polymers.EXAMPLES

[0083] All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted.

[0084] 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.

[0085] Examples 1 to 7 are synthetic procedures for ligand intermediates, ligands, and catalysts. In Example 8, the results of the polymerization reactions of metal-ligand complexes (MLC) 1-4 and comparative metal-ligand complexes (CMLC) A-D are tabulated and discussed. The structures of the MLC and CMLC of the Examples are depicted below.86264-WO-PCT / DOW 86264 WO22

[0086] One or more features of the present disclosure are illustrated in view of the examples as follows:Example 1 (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodimethylgermane [2]

[0087] A 100 mL round bottom flask was charged with the bromoarene 1 (1.48 g, 5.23 mmol, 1.00 equiv) and 35 mL dry diethyl ether. The mixture was stirred at -78 °C and n-butyllithium (2.5 M in hexane, 2.13 mL, 5.33 mmol, 1.02 equiv) was added dropwise. The mixture stirred for 120 minutes. Dichlorodimethylgermane (0.998 g, 5.75 mmol, 1.10 equiv) was injected rapidly. The mixture stirred overnight and was allowed to warm to ambient temperature. The solvent was removed by rotary evaporation, leaving a white, heterogeneous residue. The residue was transferred to a glovebox, and was diluted with 20 mL dry hexane. The slurry was fdtered to remove solids. The fdtrate was concentrated to a waxy white solid (1.70 g, 95%).

[0088] 1H NMR (400 MHz, C6D6) 8 7.50 (d, J = 2.2 Hz, 1H), 7.22 (d, J = 2.2 Hz, 1H), 5.77(ddt, J = 17.3, 10.8, 4.3 Hz, 1H), 5.51 - 5.40 (m, 1H), 5.09 (dq, J = 10.8, 1.9 Hz, 1H), 4.33 (dt, J86264-WO-PCT / DOW 86264 WO23= 4.1, 1.9 Hz, 2H), 2.13 (s, 3H), 1.39 (s, 9H), 0.86 (s, 6H).13C NMR (101 MHz, C6D6) 8 159.68, 142.20, 133.71, 133.58, 133.48, 132.77, 131.24, 115.80, 76.30, 35.03, 31.04, 20.65, 5.31.Example 2(2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)dimethyl(2-methyl-3H-cyclopenta[a]naphthalen-3- yl)germane [4] and CMLC B

[0089] In a glovebox, a 50 mL jar was charged with the indene 3 (0.831 g, 4.61 mmol, 1.05 equiv) and 30 mL dry hexane. After solids dissolved, n-butyllithium (2.5 M in hexane, 1.85 mL, 4.61 mmol, 1.05 equiv) was injected. The mixture became cloudy white and heterogeneous. After 3 hours, the germanyl chloride 2 (1.50 g, 4.39 mmol, 1.00 equiv) was added in 30 mL dry THF. The mixture stirred for 1 hour.The mixture was removed from the glovebox and was quenched with aqueous ammonium chloride. Product was extracted with portions of diethyl ether. Combined organic fractions were dried with magnesium sulfate and concentrated. The residue was purified by chromatography on silica gel (0 to 40 % dichloromethane in hexane). 1.747 g of product was isolated as a clear, colorless oil (82%).

[0090] 'H NMR (400 MHz, CDC13) 8 8.08 (d, J = 8.2 Hz, 1H), 7.83 (d, J = 8.1 Hz, 1H), 7.45 (dd, J = 8.0, 5.9 Hz, 2H), 7.41 - 7.36 (m, 1H), 7.24 (s, 1H), 7.20 (d, J = 2.1 Hz, 1H), 7.09 (s, 1H), 6.92 (d, . / = 2.2 Hz, 1H), 6.14 - 5.97 (m, 1H), 5.54 (dd, J= 17.3, 2.0 Hz, 1H), 5.33 - 5.25 (m, 1H), 4.45 (ddt, J = 14.0, 4.2, 1.9 Hz, 1H), 4.37 (ddt, J = 13.9, 4.3, 2.0 Hz, 1H), 4.26 (s, 1H), 2.27 (s, 3H), 2.02 (s, 3H), 1.43 (s, 9H), 0.33 (s, 3H), 0.10 (s, 3H).13C NMR (101 MHz, CDCI3) 8 160.44,86264-WO-PCT / DOW 86264 WO24148.15, 142.20, 142.02, 140.19, 134.09, 133.64, 133.55, 132.74, 131.79, 129.76, 128.17, 127.30, 124.81, 124.13, 123.83, 122.37, 122.19, 122.00, 116.16, 75.84, 50.16, 35.23, 31.10, 21.03, 16.98, -1.82, -3.79.

[0091] In a glovebox, a 50 mL round bottom flask was charged with the allyl ligand 4 (0.360 g, 0.742 mmol, 1.00 equiv) and 8 mL toluene. The flask was sealed and transferred to a fume hood. The solution was stirred at -78 °C under a blanket of nitrogen. Triethylamine (0.465 mL, 3.34 mmol, 4.50 equiv) was added, followed by n-butyllithium (0.623 mL, 1.56 mmol, 2.10 equiv). The cooling bath was removed and the mixture stirred at ambient temperature for 90 minutes. The solution was re-cooled to -78 °C and a solution ofTiCh (0.122 mL, 1.11 mmol, 1.50 equiv) in 1 mL toluene was added. The solution was transferred to a glovebox and was stirred at 80 °C for 4 hours. The heterogeneous mixture was cooled and filtered to remove solids. The red filtrate was concentrated to drynessThe material was triturated with hexane and dried under vacuum to give 0.120 g of the red solid. The Ti-Cl complex 5 was taken onto the next step.

[0092] 'H NMR (400 MHz, C6D6) 8 8.12 (d, J = 8.0 Hz, 1H), 7.39 (t, J = 8.0 Hz, 2H), 7.28 - 7.20 (m, 2H), 7.17 (s, 2H), 7.14 (d, J = 2.1 Hz, 2H), 2.25 (s, 3H), 2.22 (s, 3H), 1.42 (s, 9H), 0.67 (s, 3H), 0.61 (s, 3H).13C NMR (101 MHz, C6D6) 8 166.26, 142.11, 137.20, 134.05, 133.68, 132.90, 132.49, 131.74, 131.69, 130.15, 129.23, 128.95, 128.68, 124.87, 121.85, 118.23, 113.46, 34.85, 29.78, 20.94, 17.25, -0.77, -1.04.

[0093] The Ti-Cl complex 5 (0.108 g, 0.192 mmol, 1.00 equiv) was dissolved in 10 mL dry diethyl ether. The solution was chilled in a -30 °C glovebox freezer for 1 hour. The solution was stirred vigorously and methylmagnesium bromide (3.0 M in diethyl ether, 0.135 mL, 0.404 mmol, 2.10 equiv) was injected. The color lightened (pale yellow) and the mixture stirred for 30 minutes. Solvent was removed by vacuum pump and the residue was suspended in 6 mL of 4:1 toluene:hexane. The slurry was filtered through a 0.45 um syringe filter. The filtrate was concentrated and suspended in pentane. The mixture was stirred for a few minutes and volatiles were removed by vacuum pump. The pentane wash / evaporation cycle was repeated two more times. 75.4 mg of a pale yellow solid was isolated (75%).

[0094] 'H NMR (400 MHz, C6D6) 8 8.18 (d, J= 8.0 Hz, 1H), 7.58 (d, J = 7.9 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 7.33 - 7.24 (m, 5H), 7.12 (d, J = 2.1 Hz, 1H), 2.28 (s, 3H), 1.77 (s, 3H), 1.69 (s, 9H), 0.98 (s, 3H), 0.58 (s, 3H), 0.56 (s, 3H), 0.02 (s, 3H).13C NMR (101 MHz, C6D6) 8 163.07, 136.23, 135.36, 132.62, 131.85, 131.62, 131.30, 130.38, 128.84, 128.66, 128.63, 128.58, 127.15,86264-WO-PCT / DOW 86264 WO25126.58, 126.44, 124.19, 123.41, 110.82, 103.99, 60.43, 51.90, 34.98, 29.83, 20.88, 14.80, 0.05, -1.19.Example 3(2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-l- yl)germane [7] and CMLC D

[0095] In a glovebox, a 20 mL vial was charged with the chlorogermane 2 (1.06 g, 3.10 mmol,I.00 equiv) and 30 mL dry THF. This solution was treated with the solid lithium CpMe4 complex (0.398 g, 3.10 mmol, 1.00 equiv). The mixture stirred overnight. The solution was removed from the glovebox and quenched with aqueous ammonium chloride. Product was extracted with several portions of diethyl ether. Combined organic fractions were concentrated and the residue purified by chromatography on silica gel (0 to 10% EtOAc in hexane). 0.475 g of product was isolated as a colorless oil (56%).

[0096] 'H NMR (400 MHz, CDC13) 8 7.13 (d, J = 2.2 Hz, 1H), 6.97 (d, J = 2.2 Hz, 1H), 6.05 (ddt, J = 17.0, 10.6, 4.3 Hz, 1H), 5.53 (dq, J = 17.2, 1.9 Hz, 1H), 5.30 - 5.25 (m, 1H), 4.38 (dt, J = 4.1, 2.0 Hz, 2H), 3.48 (s, 1H), 2.29 (s, 3H), 1.79 (s, 6H), 1.70 (s, 6H), 1.38 (s, 9H), 0.26 (s, 6H).13C NMR (101 MHz, CDCI3) 8 160.37, 141.95, 134.74, 134.01, 133.83, 133.12, 132.36, 129.22, 116.05, 75.43, 35.16, 31.02, 21.10, 13.67, 11.04, -2.40.

[0097] In a glovebox, a 100 mL round bottom flask was charged with the allyl ligand 7 (1.06 g, 2.48 mmol, 1.00 equiv) and 25 mL dry toluene. The flask was sealed and transferred to a fume hood. The solution was stirred at -78 °C under a blanket of nitrogen. Triethylamine (1.56 mL,I I.2 mmol, 4.50 equiv) was added, followed by n-butyllithium (2.08 mL, 5.21 mmol, 2.10 equiv). The cooling bath was removed, and the mixture stirred for 90 minutes. The flask was re-cooled to86264-WO-PCT / DOW 86264 WO26-78 °C and TiCh (0.299 mL, 2.73 mmol, 1.10 equiv) in approximately 5 mL toluene was added dropwise. The mixture was warmed to room temperature and transferred to a glovebox. The flask was stirred at 80 °C for 4 hours. The slurry was fdtered to remove solids. The fdtrate was concentrated to a brown-orange solid. The solid was suspended in approximately 10 mL pentane and the mixture was stirred for a few minutes. The solvent was removed by vacuum pump. The pentane wash / evaporation cycle was repeated two more times. The orange residue was suspended in 10 mL hexane and stirred for 20 minutes. The slurry was chilled in a -30 °C freezer for 1 hour, and the mixture fdtered to isolate 0.653 g of the orange solid TiCh complex 8 (52%).

[0098] 'H NMR (500 MHz, C6D6) 8 7.16 (s, 1H), 7.05 (s, 1H), 2.23 (s, 3H), 2.03 (s, 6H), 1.93 (s, 6H), 1.58 (s, 9H), 0.50 (s, 6H).

[0099] The TiCh complex 8 (0.653 g, 1.30 mmol, 1.00 equiv) was dissolved in 25 mL diethyl ether, and the orange solution was treated with methylmagnesium brominde (3.0 M in diethyl ether, 0.907 mL, 2.72 mmol, 2.10 equiv). The mixture stirred for 2 hours and solvent was removed by vacuum pump. The residue was suspended in 25 mL of 5:1 toluene :hexane and was fdtered through a fdter frit, then a 0.45 um syringe fdter. The fdtrate was concentrated to dryness. The solid was suspended in approximately 10 mL pentane and the mixture was stirred for a few minutes. The solvent was removed by vacuum pump. The pentane wash / evaporation cycle was repeated two more times. 0.418 g of a tan-white solid was isolated (70%).

[0100] 1H NMR (400 MHz, C6D6) 8 7.26 (d, J = 2.2 Hz, 1H), 7.07 (d, J = 2.3 Hz, 1H), 2.28(s, 3H), 1.96 (s, 6H), 1.78 (s, 9H), 1.70 (s, 6H), 0.68 (s, 6H), 0.46 (s, 6H).13C NMR (101 MHz, C6D6) 8 162.74, 135.92, 133.00, 131.73, 130.85, 129.09, 128.55, 128.36, 110.27, 53.27, 35.04, 29.87, 20.89, 13.02, 11.67, -0.15.Example 4 MLC 186264-WO-PCT / DOW 86264 WO27

[0101] In a glovebox, a 50 mL round bottom flask was charged with ligand 9 (0.360 g, 0.817 mmol, 1.00 equiv) and 9 mL dry toluene. The flask was sealed and transferred to a fume hood. The solution was stirred at -78 °C under a blanket of nitrogen. Triethylamine (0.512 mL, 3.68 mmol, 4.50 equiv) was added, followed by n-butyllithium (0.686 mL, 1.72 mmol, 2.10 equiv). The cooling bath was removed, and the mixture stirred for 90 minutes. The flask was transferred to the glovebox and the solution was treated with ScC13-3THF (0.315 g, 0.858 mmol, 1.05 equiv). The flask was stirred at 80 °C for 14 hours. The mixture was filtered to remove white solids and the filtrate was concentrated to dryness. The solid was suspended in 15 mL hexane and chilled in a glovebox freezer for a few hours. The cold solution was filtered to remove a white solid. The solid was dried under vacuum to give 0.149 g of the Sc-Cl complex 10 (33%). This was used for the subsequent reaction. Proton NMR showed signals consistent with the Sc-Cl complex 10 as a single configurational isomer.

[0102] 'H NMR (400 MHz, C6D6) 8 8.29 (d, J = 8.0 Hz, 1H), 7.64 (d, J = 9.1 Hz, 1H), 7.51 (d, J = 7.9 Hz, 1H), 7.48 - 7.37 (m, 3H), 7.31 (d, . / = 2.3 Hz, 1H), 7.25 (t, J = 7.5 Hz, 1H), 7.05 (d, J = 9.2 Hz, 1H), 3.02 (s, 2H), 2.77 (d, J = 16.7 Hz, 2H), 2.38 (d, J = 3.2 Hz, 6H), 1.56 (s, 9H), 0.85 - 0.56 (m, 10H).

[0103] A 20 mL vial was charged with the Sc-Cl complex 10 (0.145 g, 0.263 mmol, 1.00 equiv) and 3 mL dry toluene. The mixture was stirred vigorously and treated with LiCH2SiMe3 (1.0 M in pentane, 0.263 mL, 0.263 mmol, 1.00 equiv). The mixture turned cloudy white and stirred for 20 minutes. The solution was filtered through a 0.45 um syringe filter. The filtrate was concentrated to dryness, approximately 3 mL pentane was added to the residue and the volatiles were removed by vacuum pump. This pentane wash / evaporation cycle was repeated two more times. The white solid was suspended in approximately 0.7 mL pentane and chilled in a glovebox freezer overnight. The liquid was removed by decantation and the solid was dried under vacuum (0.107 g, 67%). Proton NMR showed product as a roughly 1 :1 mixture of two configurational isomers.

[0104] 'H NMR (400 MHz, C6D6) 8 8.51 (d, J = 8.1 Hz, 0.5H), 8.38 (d, J = 8.0 Hz, 0.5H), 7.78 - 7.67 (m, 1.5H), 7.66 (s, 0.5H), 7.60 (d, J = 9.1 Hz, 0.5H), 7.57 - 7.46 (m, 1H), 7.46 - 7.28 (m, 3H), 7.28 - 7.20 (m, 1H), 7.00 (d, J = 9.0 Hz, 0.5H), 2.98 - 2.88 (m, 2H), 2.82 (t, J = 7.3 Hz, 1H), 2.71 (td, J = 7.3, 3.9 Hz, 1H), 2.43 (s, 1.5H), 2.38 (s, 1.5H), 2.27 (br s, 3H), 1.84 - 1.33 (m, 9H), 1.03 - 0.92 (m, 2H), 0.77 (s, 1.5H), 0.71 (m, 3H), 0.63 (br s, 1.5H), 0.41 (s, 4.5H), 0.36 (s,86264-WO-PCT / DOW 86264 WO282H), -0.11 (s, 4.5H), -0.28 (d, J = 10.8 Hz, 0.5H), -0.50 (d, J = 10.8 Hz, 0.5H), -1.54 (s, 0.5H), -2.47 (s, 0.5H).

[0105] Pre-ligand 9 was prepared using a previously published method (W02019038605).Example 5MLC 2

[0106] In a glovebox, a 50 mL round bottom flask was charged with the allyl ligand 4 (0.360 g, 0.742 mmol, 1.00 equiv) and 8 mL dry toluene. The flask was sealed and transferred to a fume hood. The solution was stirred at -78 °C under a blanket of nitrogen. Triethylamine (0.465 mL, 3.34 mmol, 4.50 equiv) was added, followed by n-butyllithium (0.623 mL, 1.56 mmol, 2.10 equiv). The cooling bath was removed, and the mixture stirred for 90 minutes. The flask was transferred to the glovebox and the solution was treated with ScC13-3THF (0.286 g, 0.779 mmol, 1.05 equiv). The flask was stirred at 80 °C for 14 hours. The slurry was filtered to remove solids. The filtrate was concentrated to a white solid. The solid was suspended in approximately 10 mL hexane and the mixture was stirred for a few minutes. The solvent was removed by vacuum pump. The hexane wash / evaporation cycle was repeated two more times. The crude Sc-Cl solid was suspended in approximately 8 mL pentane, and the heterogeneous slurry stirred for 10 minutes. The mixture was chilled in a glovebox freezer for 1 hour, and the mixture was filtered to remove the liquid. The white solid was dried under vacuum to give 0.244 g of the Sc-Cl complex in 11 (55%).

[0107] 'H NMR (400 MHz, C6D6) 8 8.31 (d, J = 8.0 Hz, 1H), 7.58 (d, J = 9.1 Hz, 1H), 7.52 (d, J= 8.0 Hz, 1H), 7.46 (s, 1H), 7.39 (t, . / = 7.6 Hz, 1H), 7.31 (d, J= 2.2 Hz, 1H), 7.30 - 7.21 (m, 2H), 7.05 (d, J= 9.1 Hz, 1H), 3.02 (s, 4H), 2.36 (s, 6H), 1.56 (s, 9H), 0.82 (2x s, 6H), 0.80 (s, 4H).13C NMR (101 MHz, C6D6) 8 162.16, 136.64, 135.83, 131.97, 130.52, 130.31, 129.72, 129.20,86264-WO-PCT / DOW 86264 WO29128.56, 126.87, 126.33, 125.07, 123.83, 123.39, 122.08, 110.03, 108.04, 72.04, 34.76, 30.02, 24.38, 20.94, 15.33, 1.05, -0.33.

[0108] The Sc-Cl solid 11 (0.244 g, 0.410 mmol, 1.00 equiv) was dissolved in 6 mL dry toluene. The mixture was stirred vigorously and was treated with LiChhSiMes (1.0 M in pentane, 0.410 mL, 0.410 mmol, 1.00 equiv). The mixture stirred for 30 minutes. Solvent was removed by vacuum pump. The residue was suspended in 5 mL of 3:1 toluene:hexane. The mixture was fdtered through a 0.45 um syringe fdter. The fdtrate was concentrated to dryness. The residue was mixed with approximately 4 mL pentane and stirred for a few minutes. Solvent was removed by vacuum pump. The pentane treatment / evaporation was repeated two more times. 0.175 g of a white solid was isolated. Proton NMR was consistent with the Sc-alkyl complex as a roughly 1 :1 mixture of configurational isomers (66%).

[0109] 'H NMR (500 MHz, CD2CI2) 5 8.32 (d, . / = 8.1 Hz, 0.5H), 8.26 (d, . / = 8.1 Hz, 0.5H), 7.79 - 7.72 (m, 1H), 7.64 (s, 0.5H), 7.61 - 7.37 (m, 3.5H), 7.29 (dd, J = 12.7, 9.1 Hz, 1H), 7.11 (s, 1H), 7.09 - 7.00 (m, 1H), 3.34 (m, 2H), 3.28 (q, J = 7.1 Hz, 1H), 2.99 (q, J = 6.8 Hz, 1H), 2.33 - 2.11 (m, 6H), 1.76 (d, J= 6.4 Hz, 2H), 1.64 - 1.47 (m, 2H), 1.44 (s, 4.5H), 1.34 (s, 10H), 0.81 - 0.69 (m, 6H), 0.01 (m, 18H), -0.42 (s, 4.5H), -0.55 (d, J = 10.6 Hz, 0.5H), -0.76 (d, J = 10.7 Hz, 0.5H), -1.82 (s, 0.5H), -2.83 (s, 0.5H).Example 6MLC 3

[0110] In a glovebox, a 50 mL round bottom flask was charged with the allyl ligand 12 (0.455 g, 1.19 mmol, 1.00 equiv) and 14 mL dry toluene. The flask was sealed and transferred to a fume hood. The solution was stirred at -78 °C under a blanket of nitrogen. Triethylamine (0.746 mL, 5.35 mmol, 4.50 equiv) was added, followed by n-butyllithium (0.999 mL, 2.50 mmol, 2.10 equiv). The cooling bath was removed, and the mixture stirred for 90 minutes. The flask was transferred to the glovebox and the solution was treated with ScC13-3THF (0.459 g, 1.25 mmol,86264-WO-PCT / DOW 86264 WO301.05 equiv). The flask was stirred at 80 °C for 14 hours. The slurry was filtered to remove solids through a medium-porosity filter. The filtrate was filtered again through a 0.45 um syringe filter. The filtrate was concentrated to an off-white solid. The solid was suspended in approximately 10 mL pentane and the mixture was stirred for a few minutes. The solvent was removed by vacuum pump. The pentane wash / evaporation cycle was repeated two more times. The final residue was suspended in 3 mL pentane and was chilled in a glovebox freezer overnight. The liquid was removed by decantation and the remaining solid was dried under vacuum to give 0.223 g of an off-white solid. (38%) Proton / Carbon NMR were consistent with the Sc-Cl complex 13.

[0111] 'H NMR (400 MHz, C6D6) 8 7.38 (d, J = 2.3 Hz, 1H), 7.31 (d, J = 2.3 Hz, 1H), 3.65 - 3.51 (m, 4H), 2.36 (s, 3H), 2.24 - 2.11 (m, 6H), 1.96 (s, 6H), 1.61 (s, 9H), 1.13 - 1.02 (m, 4H), 0.63 (s, 6H).13C NMR(101 MHz, C6D6) 8 163.94, 135.55, 132.55, 129.00, 128.26, 113.15, 71.93, 34.73, 30.04, 24.56, 21.04, 12.69, 11.46, 1.06.

[0112] The Sc-Cl complex 13 (0.223 g, 0.452 mmol, 1.00 equiv) was dissolved in 9 mL of 1 :1 toluene:THF. The mixture was chilled in a glovebox freezer for 1 hour. The solution was treated with freshly crystallized LiCH2SiMe3 (0.043 g, 0.452 mmol, 1.00 equiv). The mixture stirred for 2 hours. Solvent was removed by vacuum pump. The residue was treated with 6 mL of 3:1 toluene :hexane and filtered through a 0.45 um syringe filter. The filtrate was concentrated to dryness. The residue was suspended in approximately 10 mL pentane and stirred for a few minutes. Pentane was removed by vacuum pump. The pentane treatment / evaporation cycle was repeated two more times. The final residue was suspended in 1 mL pentane and chilled overnight in a glovebox freezer. The white slurry was filtered to remove solids. The filtrate was concentrated and the solid dried under vacuum. Proton NMR of the white solid was consistent with the desired product as a mixture of two isomers in a roughly 2:1 ratio (0.122 g, 50%).

[0113] 'H NMR (400 MHz, C6D6) 8 7.37 (dd, J = 2.3, 0.8 Hz, 0.66H), 7.31 (d, J = 2.3 Hz, 0.66H), 7.28 (d, J = 2.4 Hz, 0.33H), 7.20 (d, J = 2.3 Hz, 0.33H), 3.54 (s, 2.66H), 3.02 (s, 1.33H), 2.37 - 1.81 (m, 15H), 1.64 (s, 6H), 1.53 (s, 3H), 1.06 (s, 4H), 0.71 (s, 2H), 0.53 (m, 3H), 0.33 (s, 4H), 0.29 (s, 6H), -0.42 (d, J= 2.1 Hz, 1.33H), -0.63 (s, 0.66H).

[0114] Pre-ligand 12 was prepared using a previously published method (Journal of Organometallic Chemistry 2007, 692(19), 4059-4066).86264-WO-PCT / DOW 86264 WO31Example 7MLC 4

[0115] In a glovebox, a 50 mL round bottom flask was charged with the allyl ligand 7 (0.260 g, 0.609 mmol, 1.00 equiv) and 7 mL dry toluene. The flask was sealed and transferred to a fume hood. The solution was stirred at -78 °C under a blanket of nitrogen. Tri ethylamine (0.382 mL, 2.74 mmol, 4.50 equiv) was added, followed by n-butyllithium (0.511 mL, 1.28 mmol, 2.10 equiv). The cooling bath was removed, and the mixture stirred for 90 minutes. The flask was transferred to the glovebox and the solution was treated with ScC13-3THF (0.235 g, 0.639 mmol, 1.05 equiv). The flask was stirred at 80 °C for 14 hours. The slurry was filtered to remove solids. The filtrate was concentrated to a white solid. The solid was suspended in approximately 10 mL pentane and the mixture was stirred for a few minutes. The solvent was removed by vacuum pump. The pentane wash / evaporation cycle was repeated two more times. A sample of the dried white solid was analyzed by Proton NMR, which showed signals consistent with the Sc-Cl complex 14 (0.302 g, 92%).

[0116] 'H NMR (500 MHz, C6D6) 8 7.34 - 7.24 (m, 2H), 3.55 (d, J = 6.5 Hz, 4H), 2.35 (s, 3H), 2.19 (s, 6H), 1.95 (s, 6H), 1.61 (s, 9H), 1.16 - 1.01 (m, 4H), 0.71 (s, 6H).

[0117] The Sc-Cl complex 14 (0.215 g, 0.400 mmol, 1.00 equiv) was dissolved in 8 mL of 1 :1 toluene:THF. The mixture was chilled in a glovebox freezer for 1 hour. The solution was treated with freshly crystallized LiCH2SiMe3 (0.038 g, 0.40 mmol, 1.0 equiv). The mixture stirred for 2 hours. Solvent was removed by vacuum pump. The residue was treated with 6 mL of 3:1 toluene :hexane and filtered through a 0.45 um syringe filter. The filtrate was concentrated to dryness. The residue was suspended in approximately 1 mL pentane and stirred for a few minutes. Pentane was removed by vacuum pump. The pentane treatment / evaporation cycle was repeated two more times. The final residue was suspended in 1 mL pentane and chilled overnight in a glovebox freezer. The white slurry was filtered to remove solids. The isolated white solid was86264-WO-PCT / DOW 86264 WO32 dried under vacuum to give 0.100 g of the complex as a mixture of isomers inn a roughly 4.7:1 ratio (42%).

[0118] 'H NMR (500 MHz, Tol) 8 7.20 (s, 1.65H), 7.01 (s, 0.35H), 3.73 - 3.39 (m, 3.3H), 3.04 (s, 0.7H), 2.36 - 2.17 (m, 6.5H), 2.06 - 1.76 (m, 8,5H), 1.59 (s, 9H), 1.16 (m, 4H), 0.73 (s, 3H), 0.60 (m, 3H), 0.24 (m, 9H), -0.42 (d, . / = 11.0 Hz, 0.83H), -0.50 (d, J = 11.2 Hz, 0.83H), -0.68 (s, 0.35H).

[0119] The complex of CMLC A was prepared using published methods disclosed in WO 2019 / 038605 Al.

[0120] The complex of CMLC C was prepared using published methods disclosed in Journal of Organometallic Chemistry 2007, 692(19), 4059-4066).Example 8 Polymerization Reactions

[0121] Catalyst activity (in terms of efficiency) and resulting polymer characteristics were assessed for MLCs 1 -4 and CMLCs A-D. The polymerization reactions were carried out in a batch reactor.

[0122] The reaction conditions for the results tabulated in Table 1 is as follows: The standard ethylene-octene copolymerization batch reactor conditions of the results in Table 1 and Table 2 for polymerization reaction at 150 °C include 43 g of ethylene, 300 g of 1 octene, 500 g of Isopar E, 10 pmol of MMA03A, 310 psi reactor pressure for a reaction time of 10 minutes. The reaction conditions for Comparative A-D that included a titanium based complex also used 1.2 eq. of [HNMe(Ci8H3?)2][B(C6F5)4 activator with respect to CMLC. The standard ethylene-octene copolymerization batch reactor conditions of the results in Table 2 for polymerization reaction at 190 °C include 43 g of ethylene, a varied amount of 1 octene, 500 g of Isopar E, 10 pmol of MMA03 A, and 390 psi reactor pressure for a reaction time of 10 minutes. The reaction conditions for Comparative A-D that included a titanium based CMLC also used 1.2 eq. of [HNMe(Ci8H3?)2][B(C6F5)4 activator with respect to CMLC.

[0123] Batch Reactor Polymerization Procedure

[0124] 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 dump86264-WO-PCT / DOW 86264 WO33 valve, which empties the reactor contents into a stainless-steel dump pot, prefilled with a catalystkill 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. 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.

[0125] 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 reaction temperature to maintain reaction pressure set point. Ethylene addition amounts are monitored by a micro-motion flow meter.

[0126] The metal-ligand complex and co-catalyst components are mixed with the appropriate amount of purified toluene to achieve a solution of desired molarity. The metal-ligand complex 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.

[0127] Tables 1-2 present results of ethylene / 1 -octene copolymerization reactions for MLC-A to MLC-D and CMLC-A to CMLC-D, following the Batch Reactor Polymerization Procedure disclosed herein. Polymerization experiments were performed at polymerization temperatures of 150 °C, and 190 °C, and for each run, the catalyst efficiency and resulting polymer properties in86264-WO-PCT / DOW 86264 WO34 terms of the polydispersity index (PDI), weight-average molecular weight, and octene incorporation were determined and are reported in Tables 1-2.TABLE 1 : Batch reactor results for ethylene-octene copolymerization data at 150 °C.TABLE 2: Batch reactor results for ethylene-octene copolymerization data at 190 °C.86264-WO-PCT / DOW 86264 WO35ND = below detection limit

[0128] As shown in Table 1 and Table 2 of the batch reactor experiments (IE1 - IE12) demonstrate how the identity of the metal-ligand complex that includes a structure according to Formula (I) impacts the catalyst efficiency, and polymerization capabilities. For example, the catalyst systems comprising MLC 1-4 generally produced polymers with significantly lower amounts of octane co-monomer.

[0129] MEASUREMENT STANDARDS

[0130] HT-GPC Analysis with IR Detection of Octene Incorporation

[0131] 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) was added to each sample for use as an internal flow marker. Samples were 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 were further diluted with TCB stabilized with BHT to a concentration of 2 mg / mL. Samples (250 pL) were 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 was 24 minutes. To calibrate for molecular weight, Agilent EasiCal polystyrene standards (PS-1 and PS-2) were diluted with 1.5 mL of TCB stabilized with BHT and dissolved by stirring at 160 °C for 15 minutes. The PS standards were 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 was determined by use of a linear calibration developed by analyzing copolymers of known compositions.

[0132] 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 a86264-WO-PCT / DOW 86264 WO36 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.

[0133] 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.

[0134] 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.”

[0135] 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.

[0136] 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

86264-WO-PCT / DOW 86264 WO37CLAIMS1. A catalyst system comprising a metal-ligand complex having a structure according to Formula (I):where:M is a metal chosen from scandium or yttrium;X is chosen from silicon or germanium;L is a monodentate or bidentate ligand selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (GwCsolaryl, (C3-C3o)heteroaryl, halogen and -H;Z is a Lewis base;R1, R2, R3, and R4are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (GwCsolaryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H, wherein: R1and R2are optionally covalently linked to form an aromatic ring or a non-aromatic ring, R2and R3are optionally covalently linked to form an aromatic ring or a non-aromatic ring, and R3and R4are optionally covalently linked to form an aromatic ring or a non-aromatic ring;R5, R6, R7, and R8are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (GwCsolaryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H;R9and R10are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl, (C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H; and86264-WO-PCT / DOW 86264 WO38 each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (CT?— CXo)ary 1,(C3-C3o)heteroaryl, and -H.

2. The catalyst system of claim 1, wherein M is scandium.

3. The catalyst system of claim 1 or claim 2, wherein R1, R2, R3, and R4are independently a (Ci-C5)alkyl.

4. The catalyst system of any preceding claim, wherein R1, R2, R3, and R4are methyl.

5. The catalyst system of claim 1 or claim 2, wherein R1and R2are covalently linked to form an aromatic ring, and the metal-ligand complex has a structure according to Formula (II):where:R3, R4, R5, R6, R7, R8, R9, R10, X, L, Z, and M are defined as in Formula (I); andR11, R12, R13, and R14are independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (CT?— CXo)ary 1,(C3-C3o)heteroaryl, -ORC, -Si(Rc)3, -Ge(Rc)3, halogen, and -H;R11and R12are optionally covalently linked to form an aromatic ring or a nonaromatic ring;86264-WO-PCT / DOW 86264 WO39R12and R13are optionally covalently linked to form an aromatic ring or a nonaromatic ring; andR13and R14are optionally covalently linked to form an aromatic ring or a nonaromatic ring.

6. The catalyst system of any preceding claim, wherein at least one of R5, R6, R7, or R8is tert-butyl.

7. The catalyst system of any preceding claim, wherein R5and R7are -H.

8. The catalyst system of any preceding claim, wherein R6and R8are independently selected from (Ci-Cio)hydrocarbyl.

9. The catalyst system of any preceding claim, wherein R5and R7are -H, R6is methyl, and R8is tert-butyl.

10. The catalyst system of any preceding claim, wherein R9and R10are independently selected from (Ci-Cio)hydrocarbyl.

11. The catalyst system of any preceding claim, wherein R9and R10are methyl.

12. The catalyst system of any preceding claim, wherein L is chosen from -R'Si(Rc)3, each Rcis independently selected from the group consisting of (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, (C6_C3o)aryl, (C3-C3o)heteroaryl, and -H, and R' is independently selected from the group consisting of (Ci-C3o)hydrocarbylene, and (Ci-C3o)heterohydrocarbylene.

13. The catalyst system of any preceding claim, wherein L is chosen from -R'Si(Rc)3, each Rcis independently selected from the group consisting of (Ci-C5)hydrocarbyl and (Ci-C5)heterohydrocarbyl, and R' is independently selected from the group consisting of (Ci-C5)hydrocarbylene and (Ci-C5)heterohydrocarbylene.86264-WO-PCT / DOW 86264 WO4014. The catalyst system of any preceding claim, wherein L is -CH2Si(CH3)3.

15. The catalyst system of any preceding claim, wherein Z is a (Ci-C2o)heterohydrocarbon.

16. The catalyst system of claim 15, wherein the heteroatom of the (Ci-C2o)heterohydrocarbon is oxygen.

17. The catalyst system of any preceding claim, wherein Z is tetrahydrofuran.

18. The catalyst system of any preceding claim, wherein:L is chosen from -R'Si(Rc)3, each Rcis independently selected from the group consisting of (Ci-C5)hydrocarbyl and (Ci-C5)heterohydrocarbyl, and R' is independently selected from the group consisting of (Ci-C5)hydrocarbylene, and (Ci-C5)heterohydrocarbyleneZ is a (Ci-Cio)heterohydrocarbon;R1, R2, R3and R4are independently selected from (Ci-C5)alkyl;R5and R7are -H;R6and R8are independently selected from (Ci-Cio)hydrocarbyl; andR9and R10are independently selected from (Ci-Cio)hydrocarbyl.

19. The catalyst system of any preceding claim, wherein: L is a bidentate ligand and L and Z are covalently linked.86264-WO-PCT / DOW 86264 WO4120. The catalyst system of any preceding claim, wherein the metal-ligand complex has a structure according to any one of formulas:86264-WO-PCT / DOW 86264 WO42MLC 7, MLC 8, or combinations thereof.

21. The catalyst system of claim 20, wherein the catalyst is chosen from MLC 1 , MLC 2, MLC 3, MLC 4, or combinations thereof.

22. The catalyst system of any preceding claim, wherein the catalyst system comprises a cocatalyst component.

23. The catalyst system of claim 22, wherein the co-catalyst component comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.

24. A method of making an ethylene-based polymer, the method comprising polymerizing 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 preceding claims, wherein the polymerizing comprises solution polymerization.

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