WO2026006103A1 - Group iv cyclopentadienyl complexes bearing 2‑amino‑imidazole ligands for olefin polymerization - Google Patents

Group iv cyclopentadienyl complexes bearing 2‑amino‑imidazole ligands for olefin polymerization

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Publication number
WO2026006103A1
WO2026006103A1 PCT/US2025/034454 US2025034454W WO2026006103A1 WO 2026006103 A1 WO2026006103 A1 WO 2026006103A1 US 2025034454 W US2025034454 W US 2025034454W WO 2026006103 A1 WO2026006103 A1 WO 2026006103A1
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catalyst system
aryl
mol
ethylene
hydrocarbyl
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French (fr)
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Mary E. Garner
Brad C. Bailey
Andrew M. Camelio
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • Embodiments of the present disclosure are generally directed to catalyst systems for olefin polymerization and, more specifically, to catalyst systems including Group IV transition metal catalysts and olefin polymerization processes incorporating the same.
  • 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.
  • 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.
  • liquid diluents such as solvents
  • an alkane or isoalkane for example isobutane or Isopar E
  • Hydrogen may also be added to the reactor.
  • the catalyst systems for producing ethylene-based polymers typically include a chromium-based catalyst system, a Ziegler–Natta catalyst system, and/or a molecular (either metallocene or non-metallocene) catalyst system.
  • the reactants and the catalyst system are circulated at an elevated polymerization temperature around the reactor, thereby producing ethylene-based homopolymer or copolymer. Either periodically or continuously, part of the reaction mixture, including ethylene-based polymer product dissolved in the diluent, together with unreacted ethylene and one or more optional comonomers, is removed from the reactor.
  • the 86026-WO-PCT/DOW 86026 WO 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.
  • the reaction mixture may be sent to a second reactor, serially connected to the first reactor, where a second polyethylene fraction may be produced.
  • a second polyethylene fraction may be produced.
  • Embodiments of this disclosure include catalysts systems.
  • the catalyst system includes a procatalyst having a structure according to Formula (I): 86026-WO-PCT/DOW 86026 WO [0009]
  • M is a metal selected from titanium, zirconium, and hafnium, the metal having a formal oxidation state of +2, +3, or +4.
  • n is 1 or 2.
  • Each X is a monodentate or bidentate ligand independently selected from unsaturated (C2 ⁇ C30)hydrocarbon, unsaturated (C 2 ⁇ C 30 )heterohydrocarbon, (C 1 ⁇ C 30 )hydrocarbyl, (C 1 ⁇ C 30 )heterohydrocarbyl, (C 6 –C 30 )aryl, (C3–C30)heteroaryl, halogen, ⁇ N(R X )2, and ⁇ (CH2)wSi(R X )3, where w is 1 to 10 and each R X is independently selected from (C1 ⁇ C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C6–C30)aryl, and (C3–C30)heteroaryl.
  • R Y is (C 1 ⁇ C 30 )hydrocarbyl, (C 1 ⁇ C 30 )heterohydrocarbyl, (C 6 –C 30 )aryl, or (C 3 –C 30 )heteroaryl.
  • R 1 is (C 1 ⁇ C 50 )hydrocarbyl, (C 1 ⁇ C 50 )heterohydrocarbyl, (C 6 –C 30 )aryl, or (C3–C30)heteroaryl.
  • Each of R 2 and R 3 is independently selected from the group consisting of (C 1 ⁇ C 30 )hydrocarbyl, (C 1 ⁇ C 30 )heterohydrocarbyl, (C 6 –C 30 )aryl, (C 3 –C 30 )heteroaryl, ⁇ OR C , ⁇ Si(R C ) 3 , ⁇ Ge(R C ) 3 , halogen, and –H, wherein R 2 and R 3 are optionally covalently linked to form an aromatic or non-aromatic ring.
  • Each R C is independently selected from the group consisting of (C1 ⁇ C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, and –H.
  • Each of R 8–12 is independently selected from (C 1 –C 30 )hydrocarbyl, (C 1 ⁇ C 30 )heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, ⁇ Si(R C )3, ⁇ Ge(R C )3, and ⁇ H, wherein optionally, any of R 8-12 are covalently connected to form one or more aromatic or non-aromatic ring or multi-ring structures.
  • Embodiments of this disclosure include polymerization processes, particularly methods of making ethylene-based polymers.
  • the methods of making include polymerizing, via solution phase polymerization in a reactor, ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of the catalyst system including a procatalyst having a structure according to Formula (I). 86026-WO-PCT/DOW 86026 WO DETAILED DESCRIPTION [0012] Specific embodiments of catalyst systems will now be described. It should be understood that the catalyst systems of this disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure. Rather, embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.
  • R, Q, M, X and n as defined above; Me : methyl; Et : ethyl; Ph : phenyl; Bn: benzyl; Cy : cyclohexyl; Mes : mesityl (2,4,6-trimethylphenyl); i-Pr : iso-propyl; nBu : n-butyl; t-Bu : tert-butyl; t-Oct : tert-octyl (2,4,4-trimethylpentan-2-yl); Tf : trifluoromethane sulfonate; : Et2O : diethyl ether; THF : tetrahydrofuran; DCM or CH2Cl2 : dichloromethane; DMSO : dimethyl sulfoxide; EtOH : ethanol; DIW : deionized water;
  • spectator ligand refers to a ligand that occupies a coordination site on the metal center of a metal–ligand complex and influences the reactivity of the metal center, but remains bound and does not de-coordinate from the metal center during the course of polymerization.
  • Spectator ligands are also referred to as “ancillary ligands” and are generally less basic or less easily protonated than ligands that de-coordinate from the metal center during polymerization.
  • a “heteroleptic” metal–ligand complex refers to a metal–ligand complex bearing a spectator ligand and one or more additional ligands that are the same or different from one another.
  • a heteroleptic complex contains both a spectator ligand and a ligand that participates in chemical reactions carried out by the metal–ligand complex, such as olefin polymerization, by de-coordinating from the metal center of the metal–ligand complex.
  • the term “independently selected” followed by multiple options is used herein to indicate that the individual R groups appearing before the term, such as R 1 , R 2 , R 3 , R 4 , R 5 , and R C can be identical or different, without dependency on the identity of any other group also appearing before the term.
  • the term “procatalyst” refers to a compound that has catalytic activity when combined with an activator.
  • activator refers to a compound that chemically reacts with a procatalyst in a manner that converts the procatalyst to a catalytically active catalyst.
  • activating co-catalyst and “activator” are interchangeable terms.
  • 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.
  • a (C 1 ⁇ C 30 )alkyl is an alkyl group having from 1 to 30 carbon atoms in its unsubstituted form.
  • certain chemical groups may be substituted by one or more substituents such as R S .
  • An R S substituted 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 R S .
  • a “(C1 ⁇ C50)alkyl substituted with exactly one group R S , where R S is phenyl ( ⁇ C6H5)” may contain from 7 to 56 carbon atoms.
  • R S is phenyl ( ⁇ C6H5)
  • the minimum and maximum total number of carbon atoms of the chemical group is determined 86026-WO-PCT/DOW 86026 WO by adding to both x and y the combined sum of the number of carbon atoms from all of the carbon atom-containing substituents R S .
  • 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., R S ).
  • 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., R S ).
  • 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.
  • ⁇ H means a hydrogen or hydrogen radical that is covalently bonded to another atom.
  • hydrocarbon means a hydrocarbon radical of from 1 to 30 carbon atoms
  • (C1 ⁇ C30)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 R S or unsubstituted.
  • Examples of (C1 ⁇ C30)hydrocarbyl are unsubstituted or substituted (C1 ⁇ C30)alkyl, (C3 ⁇ C30)cycloalkyl, (C3 ⁇ C20)cycloalkyl-(C1 ⁇ C10)alkylene, (C6 ⁇ C30)aryl, or (C6 ⁇ C20)aryl-(C1-C10)alkylene (such as benzyl ( ⁇ CH2 ⁇ C6H5)).
  • Examples of (C1 ⁇ C50)hydrocarbyl are unsubstituted or substituted (C1 ⁇ C50)alkyl, (C3 ⁇ C50)cycloalkyl, (C3 ⁇ C20)cycloalkyl-(C1 ⁇ C20)alkylene, (C6 ⁇ C40)aryl, or (C 6 ⁇ C 20 )aryl-(C 1 -C 20 )alkylene (such as benzyl ( ⁇ CH 2 ⁇ C 6 H 5 )).
  • (C 1 ⁇ C 50 )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 R S .
  • alkyl groups are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more R S .
  • unsubstituted (C1 ⁇ C50)alkyl are unsubstituted (C1 ⁇ C20)alkyl; unsubstituted (C1 ⁇ C10)alkyl; unsubstituted (C1 ⁇ C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1- dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl.
  • substituted 86026-WO-PCT/DOW 86026 WO (C1 ⁇ C40)alkyl are substituted (C1 ⁇ C20)alkyl (such as benzyl ( ⁇ CH2 ⁇ C6H5)), substituted (C1 ⁇ C10)alkyl, trifluoromethyl, and [C45]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 ⁇ C40)alkyl substituted by one R S , which is a (C1 ⁇ C5)alkyl, respectively.
  • Each (C1 ⁇ C5)alkyl may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.
  • (C 6 ⁇ C 40 )aryl means an unsubstituted or substituted (by one or more R S ) 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.
  • aryl groups are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more R S .
  • a monocyclic aromatic hydrocarbon radical includes one aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic.
  • the other ring or rings of the aromatic radical may be independently fused or non-fused and aromatic or non- aromatic.
  • unsubstituted (C 6 ⁇ C 40 )aryl examples include: unsubstituted (C 6 ⁇ C 20 )aryl, unsubstituted (C 6 ⁇ C 18 )aryl; 2-(C 1 ⁇ C 5 )alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene.
  • substituted (C 6 ⁇ C 40 )aryl examples include: substituted (C 1 ⁇ C 20 )aryl; substituted (C 6 ⁇ C 18 )aryl; 2,4-bis([C 20 ]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9- one-l-yl.
  • (C3 ⁇ C50)cycloalkyl means a saturated cyclic hydrocarbon radical of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more R S .
  • cycloalkyl groups are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more R S .
  • unsubstituted (C3 ⁇ C40)cycloalkyl are unsubstituted (C3 ⁇ C20)cycloalkyl, unsubstituted (C3 ⁇ C10)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.
  • Examples of substituted (C 3 ⁇ C 40 )cycloalkyl are substituted (C 3 ⁇ C 20 )cycloalkyl, substituted (C 3 ⁇ C 10 )cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.
  • Examples of (C 1 ⁇ C 50 )hydrocarbylene include unsubstituted or substituted (C 6 ⁇ C 50 )arylene, (C 3 ⁇ C 50 )cycloalkylene, and (C 1 ⁇ C 50 )alkylene (e.g., (C 1 ⁇ C 20 )alkylene).
  • the 86026-WO-PCT/DOW 86026 WO 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 ⁇ , ⁇ -diradical, and others a 1,2-diradical.
  • the ⁇ , ⁇ -diradical is a diradical that has maximum carbon backbone spacing between the radical carbons.
  • (C2 ⁇ C20)alkylene ⁇ , ⁇ -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 (C6 ⁇ C50)arylene ⁇ , ⁇ -diradicals include phenyl-1,4-diyl, napthalen-2,6-diyl, or napthalen-3,7-diyl.
  • (C1 ⁇ C50)alkylene 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 R S .
  • Other alkylene groups e.g., (C x ⁇ C y )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 R S .
  • Examples of unsubstituted (C1 ⁇ C50)alkylene are unsubstituted (C 1 ⁇ C 20 )alkylene, including unsubstituted ⁇ CH 2 CH 2 ⁇ , ⁇ (CH 2 ) 3 ⁇ , ⁇ (CH 2 ) 4 ⁇ , ⁇ (CH 2 ) 5 ⁇ , ⁇ (CH 2 ) 6 ⁇ , ⁇ (CH 2 ) 7 ⁇ , ⁇ (CH 2 ) 8 ⁇ , ⁇ CH 2 C*HCH 3 , and ⁇ (CH 2 ) 4 C*(H)(CH 3 ), in which “C*” denotes a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical.
  • substituted (C1 ⁇ C50)alkylene examples include substituted (C1 ⁇ C20)alkylene, ⁇ CF2 ⁇ , ⁇ C(O) ⁇ , and ⁇ (CH2)14C(CH3)2(CH2)5 ⁇ (i.e., a 6,6-dimethyl substituted normal-1,20-eicosylene).
  • examples of substituted (C 1 ⁇ C 50 )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.
  • (C 3 ⁇ C 50 )cycloalkylene means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more R S .
  • Other cycloalkylene groups e.g., (C x ⁇ C y )cycloalkylene
  • heteroatom refers to an atom other than hydrogen or carbon.
  • heterohydrocarbon refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom.
  • (C 1 ⁇ C 50 )heterohydrocarbyl means a heterohydrocarbon radical of from 1 to 50 carbon atoms
  • (C1 ⁇ C50)heterohydrocarbylene means a heterohydrocarbon diradical of from 1 to 50 carbon atoms.
  • the heterohydrocarbon of the (C 1 ⁇ C 50 )heterohydrocarbyl or the (C1 ⁇ C50)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 (C 1 ⁇ C 50 )heterohydrocarbyl and (C 1 ⁇ C 50 )heterohydrocarbylene may be unsubstituted or substituted (by one or more R S ), 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
  • the (C 1 ⁇ C 50 )heterohydrocarbyl may be unsubstituted or substituted.
  • Non-limiting examples of the (C 1 ⁇ C 50 )heterohydrocarbyl include (C 1 ⁇ C 50 )heteroalkyl, (C 1 ⁇ C 50 )hydrocarbyl-O ⁇ , (C 1 ⁇ C 50 )hydrocarbyl-S ⁇ , (C 1 ⁇ C 50 )hydrocarbyl-S(O) ⁇ , (C 1 ⁇ C 50 )hydrocarbyl-S(O) 2 ⁇ , (C 1 ⁇ C 50 )hydrocarbyl-Si(R C ) 2 ⁇ , (C l ⁇ C 50 )hydrocarbyl-N(R N ) ⁇ , (C l ⁇ C 50 )hydrocarbyl-P(R P ) ⁇ , (C 2 ⁇ C 50 )heterocycloalkyl, (C 2 ⁇ C 19 )
  • the (C1 ⁇ C30)heterohydrocarbyl may be unsubstituted or substituted.
  • Non-limiting examples of the (C1 ⁇ C30)heterohydrocarbyl include (C1 ⁇ C30)heteroalkyl, (C1 ⁇ C30)hydrocarbyl-O ⁇ , (C1 ⁇ C30)hydrocarbyl-S ⁇ , (C1 ⁇ C30)hydrocarbyl-S(O) ⁇ , (C1 ⁇ C30)hydrocarbyl-S(O)2 ⁇ , (C1 ⁇ C30)hydrocarbyl-Si(R C )2 ⁇ , (Cl ⁇ C30)hydrocarbyl-N(R N ) ⁇ , (Cl ⁇ C30)hydrocarbyl-P(R P ) ⁇ , (C2 ⁇ C30)heterocycloalkyl, (C2 ⁇ C20)heterocycloalkyl- 86026-WO-PCT/DOW 86026 WO (C1
  • (C3 ⁇ C50)heteroaryl means an unsubstituted or substituted (by one or more R S ) 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.
  • 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 ⁇ C12)heteroaryl
  • (Cx ⁇ Cy)heteroaryl generally, such as (C4 ⁇ C12)heteroaryl
  • the monocyclic heteroaromatic hydrocarbon radical is a 5-membered ring or a 6-membered ring.
  • the 5-membered ring has 5 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1, 2, or 3; and each heteroatom may be O, S, N, or P.
  • Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol-1-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- 1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-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.
  • 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 1,7-dihydropyrrolo[3,2-f]indol-1-yl.
  • An Example of the fused 5,6,6-ring system is 1H-benzo[f] indol-1-yl.
  • An Example of the fused 6,5,6-ring system is 9H-carbazol-9-yl.
  • (C1 ⁇ C50)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.
  • (C1 ⁇ C50)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(R C ) 3 , Ge(R C ) 3 , Si(R C ) 2 , Ge(R C ) 2 , P(R P ) 2 , P(R P ), N(R N )2, N(R N ), N, O, OR C , S, SR C , S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups are unsubstituted or are substituted by one or more R S .
  • Examples of unsubstituted (C 2 ⁇ C 40 )heterocycloalkyl include unsubstituted (C 2 ⁇ C 20 )heterocycloalkyl, unsubstituted (C 2 ⁇ C 10 )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.
  • halogen atom or “halogen” means the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I).
  • halide means the anionic form of the halogen atom: fluoride (F ⁇ ), chloride (Cl ⁇ ), bromide (Br ⁇ ), or iodide (I ⁇ ).
  • 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.
  • one or more double and/or triple bonds optionally may or may not be present in substituents R S .
  • the term “unsaturated” means containing one or more carbon–carbon double bonds, carbon–carbon triple bonds, or (in heteroatom-containing groups) one or more carbon– nitrogen, carbon–phosphorous, or carbon–silicon double bonds, not including double bonds that may be present in substituents R S , if any, or in (hetero) aromatic rings, if any.
  • Embodiments of the catalysts systems described herein include a procatalyst having a structure according to Formula (I): 86026-WO-PCT/DOW 86026 WO [0037]
  • M is a metal selected from titanium, zirconium, and hafnium, the metal having a formal oxidation state of +2, +3, or +4.
  • n is 1 or 2.
  • Each X is a monodentate or bidentate ligand independently selected from unsaturated (C2 ⁇ C30)hydrocarbon, unsaturated (C2 ⁇ C30)heterohydrocarbon, (C1 ⁇ C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C6–C30)aryl, (C 3 –C 30 )heteroaryl, halogen, ⁇ N(R X ) 2 , and ⁇ (CH 2 ) w Si(R X ) 3 , where w is 1 to 10 and each R X is independently selected from (C 1 ⁇ C 30 )hydrocarbyl, (C 1 ⁇ C 30 )heterohydrocarbyl, (C 6 –C 30 )aryl, and (C 3 –C 30 )heteroaryl.
  • Formula (I) is overall charge neutral.
  • the presence of both the cyclopentadienyl ligand and the 2-amino-imidazole ligand on the same metal center of the catalysts described herein may be advantageous for achieving improved catalyst activity and tunable polymer properties, relative to homoleptic 2-amino-imidazole complexes wherein the ligands bonded to the metal center, other than the 2-amino-imidazole ligand, are the same (e.g., three benzyl ligands).
  • heteroleptic 2-amino-imidazole complexes described herein have increased catalyst activities relative to their homoleptic analogs while also producing polymers with low comonomer incorporation and low weight-average molecular weight, the combination of which is believed to be favorable for polymer processability.
  • the Group IV heteroleptic complexes described herein having a coordination sphere comprising both the 2-amino-imidazole ligand and the cyclopentadienyl ligand may demonstrate high activity at elevated temperatures (e.g., up to at least 150 °C) while also achieving ultra-high ethylene selectivity (e.g., resulting in ⁇ 99.5 mol% units derived from ethylene for the produced polymer). Therefore, the combination of these ligands on the same metal center creates efficient and highly ethylene-selective catalysts whose molecular weight capability can be further adjusted through synthetic modification on the 86026-WO-PCT/DOW 86026 WO overall catalyst framework.
  • R Y is (C1 ⁇ C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C6–C30)aryl, or (C 3 –C 30 )heteroaryl.
  • R 1 is (C 1 ⁇ C 50 )hydrocarbyl, (C 1 ⁇ C 50 )heterohydrocarbyl, (C 6 –C 30 )aryl, or (C3–C30)heteroaryl.
  • Each of R 2 and R 3 is independently selected from the group consisting of (C1 ⁇ C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, ⁇ OR C , ⁇ Si(R C ) 3 , ⁇ Ge(R C ) 3 , halogen, and –H, wherein R 2 and R 3 are optionally covalently linked to form an aromatic or non-aromatic ring.
  • Each R C is independently selected from the group consisting of (C1 ⁇ C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, and –H.
  • Each of R 8–12 is independently selected from (C1–C30)hydrocarbyl, (C1 ⁇ C30)heterohydrocarbyl, (C 6 –C 30 )aryl, (C 3 –C 30 )heteroaryl, ⁇ Si(R C ) 3 , ⁇ Ge(R C ) 3 , and ⁇ H, wherein optionally, any of R 8-12 are covalently connected to form one or more aromatic or non-aromatic ring or multi-ring structures.
  • each X is independently selected from (C1 ⁇ C10)alkyl, (C6 ⁇ C20)aryl, and halogen, and R 1 is (C1 ⁇ C30)alkyl or (C6 ⁇ C30)aryl.
  • n is 2.
  • n is 1.
  • n is 1or 2.
  • each X is independently selected from the group consisting of methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro.
  • R Y is (C1 ⁇ C8)alkyl.
  • R Y is methyl, ethyl, 1-propyl, 2-propyl, n-butyl, tert-butyl, 2-methylpropyl (iso-butyl), n-butyl, n-hexyl, cyclohexyl, n-octyl, tert-octyl, or benzyl.
  • R 1 is (C6 ⁇ C30)aryl.
  • R 1 is unsubstituted phenyl, substituted phenyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted naphthyl, or substituted naphthyl. In various embodiments, R 1 is unsubstituted phenyl or substituted phenyl.
  • R 1 is 2-methylphenyl, 2-(iso-propyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,6-di(iso-propyl)phenyl, 2,4,6-tri(iso-propyl)phenyl, 3,5-di(tert-butyl)phenyl, 3,5-diphenylphenyl, or 2,3,5,6-tetrafluorophenyl, or 2-(1-naphthyl)phenyl.
  • R 1 is (C1 ⁇ C12)alkyl, (C1 ⁇ C12)cycloalkyl, trimethylsilyl methyl, benzyl, or 1-adamantyl. 86026-WO-PCT/DOW 86026 WO [0044]
  • the (C1 ⁇ C30)hydrocarbyl of R 2 and R 3 may be a (C 6 ⁇ C 30 )aryl and the (C 1 ⁇ C 30 )heterohydrocarbyl of R 2 and R 3 may be a (C 3 ⁇ C 30 )heteroaryl.
  • R 2 and R 3 are covalently linked to form an aromatic ring, and the procatalyst has a structure according to Formula (II): [0046]
  • each R 1 , R Y , R 8-12 , Q, X, M, and n are defined as in Formula (I) and each of R 4 , R 5 , R 6 , and R 7 is independently (C1 ⁇ C40)hydrocarbyl, (C1 ⁇ C40)heterohydrocarbyl, (C6–C40)aryl, (C3–C40)heteroaryl, halogen, or ⁇ H.
  • each of R 5 , R 6 , and R 7 is ⁇ H.
  • R 4 is (C6 ⁇ C40)aryl or (C3 ⁇ C40)heteroaryl. In some embodiments, R 4 is (C6 ⁇ C40)aryl or (C3 ⁇ C40)heteroaryl, and each of R 5 , R 6 , and R 7 is –H.
  • R 4 is phenyl, 2,4,6-tri(iso-propyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 3,5-di(tert-butyl)phenyl, unsubstituted naphthyl, substituted naphthyl, unsubstituted carbozolyl, or substituted carbozolyl.
  • R 1 is unsubstituted phenyl or substituted phenyl.
  • R 4 is phenyl, 2,4,6-tri(iso-propyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 3,5-di(tert- butyl)phenyl, unsubstituted naphthyl, substituted naphthyl, unsubstituted carbozolyl, or substituted carbozolyl, and each of R 5 , R 6 , and R 7 is –H.
  • n is 2. In other embodiments, n is 1.
  • R 1 is (C6 ⁇ C30)aryl
  • R 4 is phenyl, 2,4,6-tri(iso-propyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 3,5-di(tert-butyl)phenyl, unsubstituted naphthyl, 86026-WO-PCT/DOW 86026 WO substituted naphthyl, unsubstituted carbozolyl, or substituted carbozolyl; and each of R 5 , R 6 , and R 7 is ⁇ H.
  • each of R 8-11 is ⁇ H and R 12 is (C1 ⁇ C10)alkyl, (C6 ⁇ C20)aryl, (C1 ⁇ C20)heterohydrocarbyl, ⁇ Si(R C )3, or ⁇ Ge(R C )3.
  • each of R 8 –R 11 is –H and R 12 is (C1 ⁇ C10)alkyl or (C6 ⁇ C20)aryl.
  • each X is identical.
  • the procatalyst may have 6 or fewer metal ⁇ ligand bonds and may be overall charge-neutral or may have a positive charge associated with the metal center.
  • the monodentate ligand may be a monoanionic ligand.
  • the bidentate ligand may be 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.
  • Each monoanionic ligand may independently be hydride, (C1 ⁇ C20)hydrocarbyl carbanion, (C1 ⁇ C20)heterohydrocarbyl carbanion, halide, nitrate, carbonate, phosphate, sulfate, HC(O)O ⁇ , HC(O)N(H) ⁇ , (C1 ⁇ C20)hydrocarbylC(O)O ⁇ , (C1 ⁇ C20)hydrocarbylC(O)N((C1 ⁇ C20)hydrocarbyl) ⁇ , (C1 ⁇ C20)hydrocarbylC(O)N(H) ⁇ , R K R L B-, R K R L N ⁇ , R K O ⁇ , R K S ⁇ , R K R L P ⁇ , or R M R K R L Si ⁇ , where each R K , R L , and R M independently is hydrogen, (C1 ⁇ C20)hydrocarbyl
  • each dianionic ligand may independently be carbonate, oxalate (i.e., ⁇ O2CC(O)O ⁇ , (C2 ⁇ C40)hydrocarbylene dicarbanion, (C1-C40)heterohydrocarbylene dicarbanion, phosphate, or sulfate.
  • at least one monodentate ligand X independently from any other ligands X, may be a neutral ligand.
  • the neutral ligand is a neutral Lewis base group such as R J NR K R L , R K OR L , R K SR L , or R J PR K R L , where each R J independently is hydrogen, [(C1 ⁇ C10)hydrocarbyl]3Si(C1 ⁇ C10)hydrocarbyl, (C1 ⁇ C20)hydrocarbyl, [(C1 ⁇ C10)hydrocarbyl]3Si, or (C1 ⁇ C20)heterohydrocarbyl and each R K and R L independently is as previously defined.
  • R J independently is hydrogen, [(C1 ⁇ C10)hydrocarbyl]3Si(C1 ⁇ C10)hydrocarbyl, (C1 ⁇ C20)hydrocarbyl, [(C1 ⁇ C10)hydrocarbyl]3Si, or (C1 ⁇ C20)heterohydrocarbyl and each R K and R L independently is as previously defined.
  • each X can be a monodentate ligand that, independently from any other ligands X, is a halogen, unsubstituted (C 1 ⁇ C 20 )hydrocarbyl, unsubstituted (C 1 ⁇ C 20 )hydrocarbylC(O)O–, or R K R L N ⁇ , wherein each of R K and R L independently is an unsubstituted(C 1 ⁇ C 20 )hydrocarbyl.
  • each monodentate ligand X is a chlorine atom, (C 1 ⁇ C 10 )hydrocarbyl (e.g., (C 1 ⁇ C 6 )alkyl or benzyl), unsubstituted (C 1 ⁇ C 10 )hydrocarbylC(O)O–, or R K R L N ⁇ , wherein each of R K and R L independently is an unsubstituted (C 1 ⁇ C 10 )hydrocarbyl.
  • X is benzyl, chloro, ⁇ CH2SiMe3, or phenyl.
  • each X is independently selected from (C 1 ⁇ C 10 )alkyl, (C6 ⁇ C20)aryl, and a halogen.
  • each X is selected from methyl; ethyl; 1-propyl; 2-propyl; 1- butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chloro.
  • each X is the same. In other embodiments, the two X ligands are different from each other.
  • X is a different one of methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2,-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chloro.
  • the bidentate ligand is 2,2-dimethyl-2-silapropane- l,3-diyl or 1,3-butadiene.
  • each X is independently selected from methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro.
  • any or all of the chemical groups (e.g., X, R 1 ⁇ R 3 , and R 8 –R 12 ) of the procatalyst of Formula (I) may be unsubstituted.
  • none, any, or all of the chemical groups X, R 1 ⁇ R 3 , and R 8 ⁇ R 12 of the procatalyst of Formula (I) may be substituted with one or more than one R S .
  • the individual R S of the chemical group may be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms.
  • none, any, or all of the chemical groups X, R 1 ⁇ R 3 , and R 8 ⁇ R 12 may be persubstituted with R S .
  • the individual R S may all be the same or may be independently chosen.
  • any or all of the chemical groups (e.g., X, R 1 , R 4 ⁇ R 7 , and R 8 –R 12 ) of the procatalyst of Formula (II) may be unsubstituted.
  • none, any, 86026-WO-PCT/DOW 86026 WO or all of the chemical groups X, R 1 , R 4 ⁇ R 7 , and R 8 –R 12 of the procatalyst of Formula (II) may be substituted with one or more than one R S .
  • the individual R S of the chemical group may be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms.
  • the catalyst systems include a procatalyst according to Formula (I) or (II) having the structure of any one of Procatalysts 1–3 below: Procatalyst 3 86026-WO-PCT/DOW 86026 WO [0062]
  • Embodiments of this disclosure include polymerization processes.
  • the polymerization processes include polymerizing, via solution phase polymerization in a reactor, ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of a catalyst system comprising a procatalyst according to Formula (I).
  • a catalyst system comprising a procatalyst according to Formula (I).
  • Co-catalyst Component the catalyst system may include a co-catalyst component.
  • the catalyst system comprising a procatalyst of Formula (I) may be rendered catalytically active by any technique known in the art for activating metal-based catalysts of olefin polymerization reactions.
  • the procatalyst according Formula (I) may be rendered catalytically active by contacting the procatalyst to, or combining the procatalyst with, one or more activating co-catalysts (also referred to herein as an “activators”).
  • the procatalyst according for Formula (I) includes both a procatalyst form, which is neutral, and a catalytic form, which may be positively charged due to the loss of a monoanionic ligand, such as benzyl or phenyl.
  • Suitable activating co-catalysts for use herein include, without limitation: alkyl aluminums; boron-based Bronsted or Lewis acids; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions); and combinations thereof.
  • a suitable activating technique is bulk electrolysis. Combinations of one or more of the foregoing activating co-catalysts and techniques are also contemplated.
  • alkyl aluminum means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum.
  • polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.
  • Lewis acid activating co-catalysts include Group 13 metal compounds containing (C 1 ⁇ C 20 )hydrocarbyl substituents as described herein.
  • Group 13 metal compounds are tri((C 1 ⁇ C 20 )hydrocarbyl)-substituted-aluminum or tri((C 1 ⁇ C 20 )hydrocarbyl)- boron compounds. In other embodiments, Group 13 metal compounds are tri(hydrocarbyl)- substituted-aluminum, tri((C 1 ⁇ C 20 )hydrocarbyl)-boron compounds, tri((C 1 ⁇ C 10 )alkyl)aluminum, tri((C 6 ⁇ C 18 )aryl)boron compounds, and halogenated (including perhalogenated) derivatives thereof.
  • Group 13 metal compounds are tris(fluoro-substituted 86026-WO-PCT/DOW 86026 WO phenyl)boranes, tris(pentafluorophenyl)borane.
  • the activating co-catalyst is a tris((C 1 ⁇ C 20 )hydrocarbyl borate (e.g. trityl tetrafluoroborate) or a tri((C 1 ⁇ C 20 )hydrocarbyl)ammonium tetra((C 1 ⁇ C 20 )hydrocarbyl)borane (e.g.
  • ammonium means a nitrogen cation that is a ((C1 ⁇ C20)hydrocarbyl)4N + a ((C 1 ⁇ C 20 )hydrocarbyl) 3 N(H) + , a ((C 1 ⁇ C 20 )hydrocarbyl) 2 N(H) 2 + , (C 1 ⁇ C 20 )hydrocarbylN(H) 3 + , or N(H) 4 + , wherein each (C 1 ⁇ C 20 )hydrocarbyl, when two or more are present, may be the same or different.
  • Combinations of neutral Lewis acid activating co-catalysts include mixtures comprising a combination of a tri((C1 ⁇ C4)alkyl)aluminum and a halogenated tri((C6 ⁇ C18)aryl)boron compound, especially a tris(pentafluorophenyl)borane.
  • Other embodiments are combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane.
  • Ratios of numbers of moles of (metal–ligand complex): (tris(pentafluoro-phenylborane): (alumoxane) are from 1:1:1 to 1:10:30, in other embodiments, from 1:1:1.5 to 1:5:10.
  • activating co-catalysts include, but are not limited to, methylaluminoxane (MAO), modified methyl aluminoxane (MMAO), triethylaluminum (TEA), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1 ⁇ ) amine (RIBS-2), and combinations thereof.
  • the activating co-catalyst comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.
  • the activating co-catalyst comprises unsubstituted ammonium borate, a mono-substituted ammonium borate, a bi-substituted ammonium borate, a tri-substituted ammonium borate, or a tetra-substituted ammonium borate.
  • the activating co-catalyst comprises bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1 ⁇ ) amine (RIBS-2).
  • more than one of the foregoing activating co-catalysts may be used in combination with each other.
  • a specific example of an activating co-catalyst combination is a mixture of a tri((C1 ⁇ C4)hydrocarbyl)aluminum, tri((C1–C4)hydrocarbyl)borane, or an ammonium borate with an oligomeric or polymeric alumoxane compound.
  • the ratio of total number of moles of one or more procatalysts of Formula (I) to total number of moles of one or more of the activating co-catalysts is from 1:10,000 to 100:1.
  • the ratio is at least 1:5,000, in some other embodiments, at least 1: 1,000; and 10:1 or less, and in some other embodiments, 1:1 or less.
  • the number of moles of the alumoxane that are employed is at least 100 times the number of moles of the procatalyst of Formula (I).
  • the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of one or more procatalysts of Formula (I) from 0.5: 1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1.
  • the remaining activating co-catalysts are generally employed in approximately mole quantities equal to the total mole quantities of one or more procatalysts of Formula (I).
  • one or more of the co-catalyst components may function as a scavenger.
  • the purpose of the scavenger is to react with any water or other impurities present in the system that might otherwise react with the catalyst leading to reduced efficiency.
  • the catalyst systems described herein may include an activator or both an activator and a scavenger.
  • the co-catalyst component includes an activator comprising unsubstituted ammonium borate, a mono-substituted ammonium borate, a bi-substituted ammonium borate, a tri-substituted ammonium borate, or a tetra-substituted ammonium borate, and a scavenger comprising methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.
  • an activator comprising unsubstituted ammonium borate, a mono-substituted ammonium borate, a bi-substituted ammonium borate, a tri-substituted ammonium borate, or a tetra-substituted ammonium borate
  • a scavenger comprising methylaluminoxane (MAO), modified methylaluminox
  • the co-catalyst component includes an activator comprising bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine (RIBS-2), and a scavenger comprising methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.
  • activator comprising bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine
  • RIBS-2 tetrakis(pentafluorophenyl)borate(1-) amine
  • a scavenger comprising methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.
  • MAO methylaluminoxane
  • the catalyst systems described herein may be supported catalyst systems wherein the procatalysts described herein, the co-catalyst component, or both, may be disposed on one or more support materials.
  • the procatalysts may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more support materials.
  • the procatalysts, the co-catalyst component, or both may be combined with one or more support materials using one of the support methods well known in the art or as described below.
  • the procatalysts, the co-catalyst component, or both may be in a supported form, for example, when deposited on, contacted with, or incorporated within, adsorbed or absorbed in, or on, one or more support materials.
  • the co-catalyst component and the support material are contacted together in an inert hydrocarbon liquid to give a suspension of a supported co-catalyst component in the inert hydrocarbon liquid, then the suspension is contacted with the procatalyst to give a suspension of the supported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed to give the supported catalyst system.
  • the removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may include a step of decanting some of the inert hydrocarbon liquid from the suspension.
  • the decanting method comprises pouring off excess inert hydrocarbon liquid from the suspension to give a concentrated suspension of the supported catalyst system.
  • the removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may comprise a step of drying the supported catalyst system.
  • the drying step may comprise a spray-drying method.
  • support materials include resinous support materials, e.g., polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • resinous support materials e.g., polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • Suitable support materials, such as inorganic oxides include oxides of metals of Group 2, 3, 4, 5, 13 or 14 of the IUPAC periodic table.
  • support materials include silica, which may or may not be dehydrated, fumed silica, alumina (e.g., as described in International Patent Application No.1999/060033), silica-alumina, and mixtures of these.
  • the fumed silica may be hydrophilic (untreated), alternatively hydrophobic (treated).
  • the support material is hydrophobic fumed silica, which may be prepared by treating an untreated fumed silica with a treating agent, such as dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane.
  • support materials include magnesia, titania, zirconia, magnesium chloride (e.g., as described in U.S. Patent No. 5,965,477), montmorillonite (e.g., as described in European Patent No. 0511665), phyllosilicate, zeolites, talc, clays (e.g., as described in U.S. Patent No. 6,034,187), and mixtures of these.
  • combinations of these support materials may be used, such as, for example, silica-chromium, silica-alumina, silica-titania, and combinations of these.
  • Additional support materials may also include those porous acrylic polymers described in European Patent No.0767184.
  • support materials may also include nanocomposites described in International Patent Application No. 1999/047598; aerogels described in International Patent Application No. 1999/048605; spherulites described in U.S. Patent No.5,972,510; and polymeric beads described in International Patent Application No. 1999/050311.
  • An example of a support material is fumed silica available under the trade name CABOSIL TS- 610, or other TS- or TG-series supports, available from Cabot Corporation. Fumed silica is typically a silica with particles 7 to 30 nanometers in size that have been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped.
  • the support material has a surface area of from 10 square meters per gram (m 2 /g) to 700 m 2 /g, a pore volume of from 0.1 cubic meters per gram (cm 3 /g) to 4.0 cm 3 /g, and an average particle size of from 5 microns ( ⁇ m) to 500 ⁇ m.
  • the support material has a surface area of from 50 m 2 /g to 500 m 2 /g, a pore volume of from 0.5 cm 3 /g to 3.5 cm 3 /g, and an average particle size of from 10 ⁇ m to 200 ⁇ m.
  • the support material may have a surface area of from 100 m 2 /g to 400 m 2 /g, a pore volume from 0.8 cm 3 /g to 3.0 cm 3 /g, and an average particle size of from 5 ⁇ m to 100 ⁇ m.
  • the average pore size of the support material is typically from 10 Angstroms ( ⁇ ) to 1,000 ⁇ , such as from 50 ⁇ to 500 ⁇ or from 75 ⁇ to 350 ⁇ .
  • the support material may comprise silica, alternatively amorphous silica (not quartz), alternatively a high surface area amorphous silica, e.g., from 500 to 1000 m 2 /g.
  • Such silicas are commercially available from several sources including the Davison Chemical Division of W.R. Grace and Company, e.g., Davison 952 and Davison 955 products, and PQ Corporation, e.g., ES70 product.
  • the silica may be in the form of spherical particles, which may be obtained by a spray-drying process.
  • MS3050 product is a silica from PQ Corporation that is not spray-dried.
  • these silicas are not calcined (i.e., not dehydrated). Silica that is calcined prior to purchase may also be used as the support material.
  • the solid support is a hydrophobic fumed silica.
  • the hydrophobic fumed silica is made by contacting an untreated fumed silica, having surfaces containing silicon- bonded hydroxyl groups (Si-OH groups), with a hydrophobing agent, described later.
  • the hydrophobing agent is a silicon-based hydrophobing agent, containing on average per molecule one or more functional groups reactive with a Si-OH group, to give the hydrophobic fumed silica.
  • the silicon-based hydrophobing agent may be selected from (CH 3 ) 2 SiCl 2 , a polydimethylsiloxane, hexamethyldisilazane (HMDZ), and a (C1–C10)alkyl-Si((C1–C10)alkoxy)3 (e.g., an octyltrialkoxysilane such as octyltriethoxysilane, i.e., CH3(CH2)7Si(OCH2CH3)3).
  • the silicon-based hydrophobing agent is dimethyldichlorosilane, i.e., (CH 3 ) 2 SiCl 2 .
  • the support material is a dimethyldichlorosilane-treated fumed silica, such as that sold as product TS-610 from Cabot Corporation.
  • the support material may be uncalcined or calcined.
  • the calcined support material is made prior to being contacted with a procatalyst, co-catalyst component, and/or hydrophobing agent, by heating the support material in air to give a calcined support material.
  • the calcining comprises heating the support material at a peak temperature from 350 °C to 850 °C, alternatively from 400 °C to 800 °C, alternatively from 400 °C to 700 °C, alternatively from 500 °C to 650 °C and for a time period from 2 to 24 hours, alternatively from 4 to 16 hours, alternatively from 8 to 12 hours, alternatively from 1 to 4 hours, thereby making the calcined support material. If the support material has not been heated in this way it is an uncalcined support material.
  • 86026-WO-PCT/DOW 86026 WO Polymerization Processes [0084] As noted above, embodiments of this disclosure include polymerization processes.
  • the polymerization processes include polymerizing, via solution phase polymerization in a reactor, ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of a catalyst system comprising a procatalyst 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.
  • the ethylene-based polymer may be produced via solution polymerization.
  • 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 optionally one or more ⁇ -olefins are polymerized in the presence of the catalyst system, as described herein, and optionally one or more co-catalysts.
  • 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 optionally one or more ⁇ -olefins are polymerized in the presence of the catalyst system in this disclosure.
  • the catalyst system as described herein, can be used in the first reactor, or second reactor, optionally in combination with one or more other catalysts.
  • 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 optionally one or more ⁇ -olefins are polymerized in the presence of the catalyst system, as described herein, in both reactors.
  • 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 optionally one or more ⁇ -olefins are polymerized in the presence of the catalyst system, as described within this disclosure, and optionally one or more co-catalyst components, as described in the preceding paragraphs. 86026-WO-PCT/DOW 86026 WO [0087]
  • methods for producing the ethylene-based polymer may include feeding hydrogen into the reactor during solution phase polymerization.
  • the ethylene-based polymers may further comprise one or more additives.
  • Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof.
  • the ethylene based-polymers may contain any amounts of additives.
  • the ethylene-based polymers may compromise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the ethylene-based polymers and the one or more additives.
  • the ethylene-based polymers may further comprise fillers, which may include, but are not limited to, organic or inorganic fillers.
  • the ethylene based-polymers may contain from about 0 to about 20 weight percent fillers such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the combined weight of the ethylene-based polymers and all additives or fillers.
  • the ethylene-based polymers may further be blended with one or more polymers to form a blend.
  • a method of making an ethylene-based polymer may include polymerizing ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer in the presence of a catalyst system, wherein the catalyst system incorporates at least procatalyst of Formula (I).
  • ⁇ -olefin 1-alkene
  • additional ⁇ -olefins may be incorporated into the polymerization procedure.
  • the additional ⁇ -olefin comonomers typically have no more than 20 carbon atoms.
  • the ⁇ -olefin comonomers may have 3 to 10 carbon atoms or 3 to 8 carbon atoms.
  • Exemplary ⁇ -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.
  • the one or more ⁇ -olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or in the alternative, from the group consisting of 1-hexene and 1-octene.
  • the ethylene-based polymers for example homopolymers and/or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as ⁇ -olefins, may comprise from at least 50 percent by weight monomer units derived from ethylene, based on a total weight of the ethylene-based polymer.
  • the ethylene-based polymers, homopolymers and/or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as ⁇ -olefins may comprise at least 60 weight percent monomer units derived from ethylene; at least 70 weight percent monomer units derived from ethylene; at least 80 weight percent monomer units derived from ethylene; or from 50 to 100 weight percent monomer units derived from ethylene; or from 80 to 100 weight percent units derived from ethylene.
  • ethylene-based polymer 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).
  • LDPE Low Density Polyethylene
  • LLDPE Linear Low Density Polyethylene
  • ULDPE Ultra Low Density Polyethylene
  • VLDPE Very Low Density Polyethylene
  • m-LLDPE linear low Density Polyethylene
  • MDPE Medium Density Polyethylene
  • HDPE High Density Polyethylene
  • the ethylene-based polymers may comprise at least 90 mole percent (mol%) units derived from ethylene. All individual values and subranges from at least 90 mol% are included herein and disclosed here
  • the ethylene-based polymers may comprise at least 93 mol% units derived from ethylene, at least 95 mol% units derived from ethylene, at least 96 mol% units derived from ethylene, at least 97 mol% units derived from ethylene, at least 98 mol% units derived from ethylene, at least 99 mol% units derived from ethylene, at least 99.5 mol% units derived from ethylene, or at least 99.9 mol% units derived from ethylene.
  • the ethylene-based polymers may comprise from 90 to 100 mol% units derived from ethylene, from 95 to 100 mol% units derived from ethylene, from 97 to 100 mol% units derived from ethylene, from 98 to 100 mol% units derived from ethylene, from 99 to 100 mol% units derived from ethylene, from 99.5 to 100 mol% units derived from ethylene, or from 99.95 to 100 mol% units derived from ethylene.
  • the ethylene-based polymers may comprise from 90 to 99.95 mol% units derived from ethylene, from 95 to 99.95 mol% units derived from ethylene, from 97 to 99.95 mol% units derived from ethylene, from 98 to 99.95 mol% units derived from ethylene, from 99 to 99.95 mol% units derived from ethylene, or from 99.5 to 99.95 mol% units derived from ethylene, or from 99.9 to 99.95 mol% units derived from ethylene.
  • the ethylene-based polymers may comprise at most 50 mol% units derived from at least one ⁇ -olefin comonomer.
  • the ethylene-based polymers may comprise at most 25 mol% units derived from at least one ⁇ -olefin comonomer, at most 10 mol% units derived from at least one ⁇ -olefin comonomer, at most 8 mol% units derived from at least one ⁇ -olefin comonomer, at most 5 mol% units derived from at least one ⁇ -olefin comonomer, at most 4 mol% units derived from at least one ⁇ -olefin comonomer, at most 3.6 mol% units derived from at least one ⁇ -olefin comonomer, at most 3 mol% units derived from at least one ⁇ -olefin comonomer, at most 2.5 mol% units derived from at least one ⁇ -olefin comonomer, at most 2.1 mol% units derived from at least one ⁇ -olefin comonomer, at most 2 mol
  • the ethylene-based polymers may comprise from 0.05 mol% to 4 mol% units derived from at least one ⁇ -olefin comonomer, from 0.05 mol% to 3.6 mol% units derived from at least one ⁇ -olefin comonomer, from 0.05 mol% to 3 mol% units derived from at least one ⁇ -olefin comonomer, from 0.05 mol% to 2.5 mol% units derived from at least one ⁇ - olefin comonomer, from 0.05 mol% to 2.1 mol% units derived from at least one ⁇ -olefin comonomer, from 0.05 mol% to 2 mol% units derived from at least one ⁇ -olefin comonomer, from 0.05 mol% to 1.8 mol% units derived from at least one ⁇ -olefin comonomer, from 0.05 mol% to 1.6 mol% units derived from
  • the additional ⁇ -olefin comonomer include 1-butene, 1-hexene, or 1-octene. In some embodiments, the additional ⁇ -olefin comonomer includes 1-octene.
  • the ethylene-based polymer polymerized in the presence of a catalyst system described herein including procatalyst of Formula (I) may have a density according to ASTM D792 (incorporated herein by reference in its entirety) from 0.850 g/cm 3 to 0.970 g/cm 3 , 0.870 g/cm 3 to 0.950 g/cm 3 , from 0.880 g/cm 3 to 0.920 g/cm 3 , from 0.880 g/cm 3 to 0.910 g/cm 3 , 0.900 g/cm 3 to 0.950 g/cm 3 , 0.920 g/cm 3 to 0.950 g/cm 3 , from 0.950 g/cm 3 to 0.970 g/cm 3 , or from 0.880 g/cm 3 to 0.900 g/cm 3 , for example.
  • the ethylene-based polymer polymerized in the presence of a catalyst system described herein including procatalyst of Formula (I) has a melt flow ratio (I 10 /I 2 ) from 5 to 15, in which melt index I2 is measured according to ASTM D1238 (incorporated herein by reference in its entirety) at 190 °C and 2.16 kg load, and melt index I10 is measured according to ASTM D1238 at 190 °C and 10 kg load.
  • melt flow ratio (I 10 /I 2 ) is from 5 to 10
  • the melt flow ratio is from 5 to 9.
  • the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a weight-average molecular weight of less than 450,000 g/mol, less than 425,000 g/mol, less than 400,000 g/mol, less than 375,000 g/mol, less than 350,000 g/mol, less than 275,000 g/mol, less than 225,000 g/mol, less than 200,000 g/mol, less than 175,000 g/mol, less than 150,000 g/mol, less than 125,000 g/mol, less than 100,000 g/mol, less than 75,000 g/mol, or even less than 50,000 g/mol.
  • the polymer resulting from the catalyst system that includes the procatalyst of Formula (I) has a weight-average molecular weight from 300 g/mol to 450,000 g/mol, from 300 g/mol to 425,000 g/mol, from 300 g/mol to 400,000 g/mol, from 300 g/mol to 375,000 g/mol, from 300 g/mol to 350,000 g/mol, from 300 g/mol to 325,000 g/mol, from 300 g/mol to 300,000 g/mol, from 300 g/mol to 275,000 g/mol, from 300 g/mol to 250,000 g/mol, from 300 g/mol to 225,000 g/mol, from 300 g/mol to 200,000 g/mol, from 300 g/mol to 175,000 g/mol, from 86026-WO-PCT/DOW 86026 WO 300 g/mol to 150,000 g/mol, from 300 g/mol to 125,000 g/mol, from 300 g/mol/
  • 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 M w /M n with M w being a weight-average molecular weight and M n being a number-average molecular weight.
  • PDI polydispersity index
  • the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI from 1 to 50.
  • the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a PDI from 1 to 20.
  • 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.
  • 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. [0100] One or more features of the present disclosure are illustrated in view of the examples as follows: EXAMPLES [0101] All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. All commercial chemicals were used without further purification.
  • Anhydrous toluene, hexanes, tetrahydrofuran, and diethyl ether were purified via passage through activated alumina and, in some cases, Q-5 reactant (also known as Q5). Solvents used for experiments performed in a nitrogen-filled glovebox were further dried by storage over activated 3 ⁇ molecular sieves. Trichloride metal precursors CpZrCl3, nBu CpZrCl3, and Me CpZrCl3 were purchased from either Strem Chemicals or Sigma Aldrich, or they were prepared according to the procedure in WO2016/168448. Glassware for moisture-sensitive reactions was dried in an oven overnight prior to use.
  • LC-MS analyses were performed using a Waters e2695 Separations Module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector.
  • LC-MS separations were performed on an XBridge C183.5 ⁇ m 2.1x50 mm column using a 5:95 to 100:0 acetonitrile to water gradient with 0.1% formic acid as the 86026-WO-PCT/DOW 86026 WO ionizing agent.
  • Examples 1 to 18 are synthetic procedures for ligand intermediates, ligands, monoanionic spectator ligands, heteroleptic metal precursors, and isolated procatalysts. In Example 19, the results of PPR Screening Experiments and batch reactor polymerization tests are tabulated and discussed.
  • Example 2 N-isopropyl-2',4',6'-trimethyl-2-nitro-[1,1'-biphenyl]-3-amine [0106]
  • 3-fluoro-2',4',6'-trimethyl-2-nitro-1,1'-biphenyl (2.60 g, 10.0 mmol, 1 equiv) was combined with DMSO (20 mL) and a magnetic stir bar in a 50 mL round bottom flask. The mixture was allowed to stir gently while K2CO3 (4.16 g, 30.1 mmol, 3 equiv) and iso- propylamine (6.03 mL, 70.2 mmol, 7 equiv) were added.
  • the reaction mixture was then heated to 80 °C and stirred for 18 h. After cooling to ambient temperature, the mixture was diluted with water (10 mL), transferred to a separatory funnel, and extracted with ethyl acetate (3 x 100 mL). The combined organic extracts were then dried with MgSO4, filtered, and concentrated to a bright red-orange oil. The oil was taken up in Et 2 O, washed with DIW and brine, dried over MgSO 4 , and filtered. The filtrate was concentrated to a bright red-orange oil that then solidified upon standing. The solids were analyzed by NMR, which confirmed the target product identity and purity. Yield: 2.5 g, 83.6 %.
  • Example 3 1-isopropyl-4-mesityl-1H-benzo[d]imidazole [0108]
  • N-isopropyl-2',4',6'-trimethyl-2-nitro-[1,1'-biphenyl]-3-amine (1.00 g, 3.35 mmol, 1 equiv) was combined with THF (14 mL), EtOH (14 mL), iron powder (0.94 g, 16.8 mmol, 5 equiv), and a magnetic stir bar at ambient temperature in a 100 mL round bottom flask.
  • Example 4 2-bromo-1-isopropyl-4-mesityl-1H-benzo[d]imidazole [0110]
  • 1-isopropyl-4-mesityl-1H-benzo[d]imidazole (1.61 g, 5.78 mmol, 1 equiv) was combined with THF (20 mL) and a magnetic stir bar in a 60 mL glass vial with a septa cap.
  • N-bromosuccinimide (1.08 g, 6.07 mmol, 1.05 equiv) was added at ambient temperature. The reaction mixture was then heated at reflux for 4 h.
  • the plug was additionally washed with ethyl acetate (30 mL) and the filtrate and washes were combined. Volatiles were removed in vacuo and the crude material was purified by column chromatography using a 0 to 10 % gradient of ethyl acetate in hexanes. The target product was isolated as a yellow oil that solidified upon standing. Yield: 0.180 g, 75.2 %.
  • Ligand 2 (L-2) - N-benzyl-1-isopropyl-4-mesityl-1H-benzo[d]imidazol-2-amine [0114] Ligand 2 was prepared in accordance with Example 52 of WO 2020/263790 A1.
  • Ligand 3 (L-3) - N-cyclohexyl-1-isopropyl-4-mesityl-1H-benzo[d]imidazol-2-amine [0116] Ligand 3 was prepared in accordance with Example 54 of WO 2020/263790 A1.
  • Ligand 4 (L-4) - 1-isopropyl-4-mesityl-N-pentyl-1H-benzo[d]imidazol-2-amine [0118] Ligand 4 was prepared in accordance with Example 55 of WO 2020/263790 A1.
  • Tricyclohexyl-phosphinimine (Cy 3 PNH) [0120] In a glovebox, tricyclohexylphosphine (0.750, 2.67 mmol, 1 equiv) was added to a 40 mL glass vial along with a magnetic stir bar and toluene (6 mL) at ambient temperature. Trimethylsilyl azide (0.531 mL, 4.01 mmol, 1.5 equiv) was added dropwise at ambient temperature while maintaining gentle stirring. After the addition was complete, the reaction was heated to 85 °C for 18 h.
  • Trimethylsilyl azide (1.03 mL, 7.72 mmol, 3.0 equiv) was added dropwise at ambient temperature while maintaining gentle stirring. After the addition was complete, the reaction was heated to 120 °C with a reflux condenser in place for 14 h. The volatiles were removed by vacuum and the resulting colorless, waxy solid was dissolved in toluene (5 mL) and methanol (2 mL) was added. The mixture was stirred for 2 h at ambient temperature. The volatiles were removed under vacuum and the resulting residue was suspended in hexanes and stored in the refrigerator overnight. The insoluble material was collected on a filter and washed with additional portions of cold hexanes. Yield: 0.814 g, 78.4%.
  • Example 12 IPrNZrBn3 [0126] In a glovebox, a 20 mL vial was charged with ZrBn 4 (0.500 g, 0.875 mmol, 1 equiv), 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPrNH) (0.442 g, 0.875 mmol, 1 equiv), and toluene (5mL). The mixture was stirred for 18 h at room temperature, followed by filtration concentration under vacuum. The resulting material was triturated with hexanes (5 mL), collected by filtration, washed with hexanes, and dried under vacuum, affording a yellow solid.
  • ZrBn 4 0.500 g, 0.875 mmol, 1 equiv
  • IPrNH 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene
  • IPrNH 1,3-bis(2,
  • the golden yellow filtrate was concentrated under vacuum, affording a bright yellow solid that was triturated with hexanes (2 ⁇ 10 mL) and washed with hexanes (2 ⁇ 20 mL).
  • the bright yellow solid was then extracted into in toluene (2 x 20 mL) and concentrated to 10 mL prior to storage at ⁇ 25 °C for 48 h.
  • Yellow crystals were collected by separating the mother liquor and washing the crystals with hexanes (1.5 mL). The crystals were dried under vacuum. Yield: 1.20 g, 63.9 %.
  • Example 14 n Bu CpZrBn3 [0130] In a nitrogen filled glovebox, nBu CpZrCl 3 (1.03 g, 3.23 mmol, 1 equiv), a magnetic stir bar, and toluene (30 mL) were combined in a 50 mL glass jar and stored at ⁇ 25 °C for 60 min. Separately, a 1.0 M solution of BnMgCl in diethyl ether (10.0 mL, 10.0 mmol, 3.1 equiv) was added to a 20 mL vial with toluene (5 mL) and also stored at ⁇ 25 °C for 60 min.
  • the material was then extracted into toluene (15 mL), filtered, and concentrated.
  • the golden-yellow filtrate was stored at ⁇ 25 °C overnight leading to the formation of golden-yellow crystals.
  • the crystals were collected by decanting the mother liquor, rinsing the crystals with a minimal amount of hexanes, and drying in vacuo. Only a single crop of crystals was collected. Yield: 0.355 g, 44.3%.
  • PPR parallel pressure reactor
  • the PPR system is composed of an array of 48 single-cell (6 x 8 matrix) reactors in an inert-atmosphere glovebox. Each cell is equipped with a glass insert with an internal working liquid volume of approximately 5 mL. Each cell has independent controls for pressure, and the liquid in the cell is continuously stirred at 800 rpm. Catalyst solutions, unless otherwise noted, are prepared in toluene.
  • All liquids for example, solvent, 1-octene, and catalyst solutions
  • Gaseous reagents for example, ethylene, CO
  • the reactors Prior to each run, the reactors are heated to 80 °C, purged with ethylene, and vented. [0141] The reactors are heated to the run temperature and pressured to the appropriate psig with ethylene. A portion of Isopar-E is added to the reactors.
  • Toluene solutions of reagents are added in the following order: (1) 1-octene with 500 nmol of scavenger MMAO-3A; (2) 1.5 equivalents activator (RIBS-II); and (3) catalyst (20 or 100 nmol).
  • Each liquid addition is chased with a small amount of Isopar E so that after the final addition a total reaction volume of 5 mL is reached.
  • the PPR software begins monitoring the pressure of each cell.
  • the desired pressure (within approximately 2–6 psig) is maintained by the supplemental addition of ethylene gas by opening the valve at the set point minus 1 psi and closing it when the pressure reached 2 psi higher.
  • Both the reactor and the heating/cooling system are controlled and monitored by a CamileTM 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. 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 reactant.
  • the ethylene is passed through two columns, the first containing A204 alumina and 4 ⁇ mol sieves, the second containing Q5 reactant.
  • the N2, used for transfers, is passed through a single column containing A204 alumna, 4 ⁇ mol sieves and Q5.
  • the reactor is loaded first from the shot tank that contains Isopar E solvent and/or 1-octene, depending on desired reactor loading.
  • the shot tank is filled to the load set points by use of a lab scale to which the shot tank is mounted. After liquid feed addition, the reactor is heated up to the polymerization temperature set point.
  • ethylene is used, it is added to the reactor when at reaction temperature to maintain reaction pressure set point. Ethylene addition amounts are monitored by a micro-motion flow meter.
  • the catalyst and co-catalyst components are mixed with the appropriate amount of purified toluene to achieve a solution of the 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 was used, it is then added by the Camile to maintain reaction the pressure set point in the reactor.
  • Table 1 presents results of polymerization reactions following the general procedure for the PPR Screening Experiments disclosed herein for various 2-amino-imidazole ligand / heteroleptic cyclopentadienyl metal precursor pairs, comparative 2-amino-imidazole ligand / heteroleptic non-cylcopentadienyl metal precursor pairs, as well as for comparative 2-amino-imidazole ligand / homoleptic metal precursor pairs.
  • TABLE 1 PPR data (averaged over duplicate runs) for various 2-amino-imidazole ligand / heteroleptic and homoleptic metal precursor pairs.
  • the reaction conditions for the results tabulated in Table 2 are as follows: the standard ethylene-octene copolymerization semi-batch reactor conditions of the results in Table 2 for polymerization reaction at 120 °C include 46 g of ethylene, 302 g of 1-octene, 612 g of Isopar E, 1.2 eq. of RIBS-2 activator with respect to catalyst, 10 ⁇ mol of MMAO-3A, 290 psi reactor pressure; the standard ethylene-octene copolymerization semi-batch reactor conditions of the results in Table 2 for polymerization reaction at 150 °C include 43 g of ethylene, 301 g of 1-octene, 548 g of Isopar E, 1.2 eq.
  • heteroleptic 2-amino-imidazole cyclopentadienyl complexes described herein demonstrate the ability for improved catalyst activity relative to their homoleptic analogs and relative to heteroleptic 2-amino-imidazole non-cyclopentadienyl complexes. It should further be noted that significantly higher loadings of the homoleptic precursors were used to achieve catalyst activity further indicating the higher activity of the inventive heteroleptic complexes.
  • IE1 (cyclopentadienyl precursor nBu CpZrBn3 combined with L-1) has higher PPR catalyst activity than comparatives CE2 and CE3 and comparable activity to CE1, where each of CE1–CE3 have the same L-1 ligand but lack a cyclopentadienyl ligand. It should further be noted that significantly higher loadings of the homoleptic precursors were used to achieve catalyst activity further indicating the higher activity of the inventive heteroleptic complexes.
  • IE2 (cyclopentadienyl precursor nBu CpZrBn 3 combined with L-2) has higher PPR catalyst activity than comparatives CE4–CE6 which have the same L-2 ligand but lack a cyclopentadienyl ligand.
  • IE3 (cyclopentadienyl precursor nBu CpZrBn 3 combined with L-3) has higher PPR catalyst activity than comparatives CE7–CE9 which have the same L-3 ligand but lack a cyclopentadienyl ligand.
  • IE4 (cyclopentadienyl precursor nBu CpZrBn 3 combined with L-4) has higher PPR catalyst activity than comparatives CE10–CE12 which have the same L-4 ligand but lack a cyclopentadienyl ligand.
  • Table 2 of the semi-batch reactor experiments (IE5–IE10) show how the heteroleptic 2-amino-imidazole cyclopentadienyl complexes described herein achieve high catalyst activity and efficiency even at elevated reactor temperatures.
  • IE5, IE7, and IE9 show how Procatalysts 1–3 all have 120 °C activity ⁇ 160,000 g poly/g metal.
  • IE6, IE8, and IE10 show how Procatalysts 1–3 all have 150 °C activity ⁇ 180,000 g poly/g metal. Additionally, the data presented in Table 2 of the semi-batch reactor experiments (IE5–IE10) show how the heteroleptic 2-amino-imidazole cyclopentadienyl complexes described herein also achieve high ethylene selectivity, as evidenced by the low 1-octene incorporation levels. IE5–10 show how Procatalysts 1–3 all have ultra-low 1-octene incorporation levels of less than or equal to 0.1 mol% and high Tm at both 120 °C and 150 °C reactor temperatures.
  • the weight-average molecular weights of the resulting polymer ranged from 48,000 to 210,000 g/mol.
  • the polydispersity index of the resulting polymer ranged from 4.7 to 8.9. Accordingly, the semi-batch reactor results show that the heteroleptic 2-amino-imidazole cyclopentadienyl complexes described herein allow for further control of polymer properties.
  • T m Melt temperatures
  • T g glass transition temperatures
  • Mw, Mn, and Polydispersity Index 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.
  • RAD Dow Robot Assisted Delivery
  • IR5 PolymerChar infrared detector
  • Agilent PLgel Mixed A columns [0159] Decane (10 ⁇ L) 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.
  • TAB 1,2,4-trichlorobenzene
  • BHT butylated hydroxytoluene
  • Samples Prior to injection samples are further diluted with TCB stabilized with BHT to a 86026-WO-PCT/DOW 86026 WO concentration of 2 mg/mL.
  • Samples 250 ⁇ L are eluted through one PL-gel 20 ⁇ m (50 x 7.5 mm) guard column followed by two PL-gel 20 ⁇ m (300 x 7.5 mm) Mixed-A columns maintained at 160 °C with TCB stabilized with BHT at a flowrate of 1.0 mL/min. The total run time is 24 minutes.

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Abstract

Catalyst systems comprising a procatalyst having a structure according to Formula (I): where M is a metal selected from titanium, zirconium, and hafnium, the metal having a formal oxidation state of +2, +3, or +4; each X is a monodentate or bidentate ligand; n is 1 or 2; each of R8–12 is independently selected from (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–‍C30)aryl, (C3–‍C30)heteroaryl, −Si(RC)3, −Ge(RC)3, and −H, wherein optionally, any of R8-12 are covalently connected to form one or more aromatic or non-aromatic ring or multi-ring structures; RY is (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–‍C30)aryl, or (C3–‍C30)heteroaryl; R1 is (C1−‍C50)hydrocarbyl, (C­1-C50)heterohydrocarbyl, (C6–‍C30)aryl, or (C3–‍C30)heteroaryl; each of R2 and R3 is independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–‍C30)aryl, (C3–‍C30)heteroaryl, −ORC, −Si(RC)3, −Ge(RC)3, halogen, and −H, wherein R2 and R3 are optionally covalently linked to form an aromatic or non-aromatic ring.

Description

86026-WO-PCT/DOW 86026 WO GROUP IV CYCLOPENTADIENYL COMPLEXES BEARING 2-AMINO-IMIDAZOLE LIGANDS FOR OLEFIN POLYMERIZATION CROSS REFERENCE TO RELATED APPLICATION [0001] This application claims priority to U.S. Provisional Application Serial No. 63/665,580 filed June 28, 2024, the entire disclosure of which is hereby incorporated by reference. TECHNICAL FIELD [0002] Embodiments of the present disclosure are generally directed to catalyst systems for olefin polymerization and, more specifically, to catalyst systems including Group IV transition metal catalysts and olefin polymerization processes incorporating the same. BACKGROUND [0003] Olefin-based polymers such as polyethylene and ethylene-based polymers are produced via various catalyst systems. Selection of such catalyst systems used in the polymerization process of the olefin-based polymers is an important factor contributing to the characteristics and properties of such olefin-based polymers. [0004] Ethylene-based polymers are manufactured for a wide variety of articles. The polymerization process for ethylene-based polymers can be varied in a number of respects to produce a wide variety of resultant polymer resins having different physical properties that render the various resins suitable for use in different applications. The ethylene monomers and, optionally, one or more comonomers, are present in liquid diluents (such as solvents), such as an alkane or isoalkane, for example isobutane or Isopar E in a solution polymerization reactor, or are present as gases in a gas-phase polymerization reactor. Hydrogen may also be added to the reactor. [0005] The catalyst systems for producing ethylene-based polymers typically include a chromium-based catalyst system, a Ziegler–Natta catalyst system, and/or a molecular (either metallocene or non-metallocene) catalyst system. The reactants and the catalyst system are circulated at an elevated polymerization temperature around the reactor, thereby producing ethylene-based homopolymer or copolymer. Either periodically or continuously, part of the reaction mixture, including ethylene-based polymer product dissolved in the diluent, together with unreacted ethylene and one or more optional comonomers, is removed from the reactor. The 86026-WO-PCT/DOW 86026 WO 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] Despite previous research efforts in developing catalyst systems suitable for olefin polymerization, such as the polymerization of ethylene-based polymers, there is still a need for catalyst systems that can be tuned to influence resulting polymer properties while also having the ability to achieve high catalyst activity. Further, catalyst systems that can achieve high catalyst activity at elevated temperatures (e.g., up to at least 150 °C) while also having the ability to copolymerize ethylene-based polymers with high ethylene selectivity and low weight-average molecular weight are of particular interest. [0007] It has now been discovered that Group IV heteroleptic complexes bearing a 2-amino-imidazole ligand in combination with a cyclopentadienyl ligand are able to address this need. In particular, it has been found that, relative to their homoleptic analogs, the heteroleptic 2-amino-imidazole complexes described herein demonstrate increased catalyst activity for olefin polymerization under commercially relevant process conditions and have the ability to produce polymers with differentiated weight-average molecular weight (Mw) , polydispersity (PDI), and comonomer incorporation, including polymers with low comonomer incorporation and low weight-average molecular weight. Moreover, by tuning the catalyst structure with respect to the substituents of the 2-amino-imidazole ligand and the cyclopentadienyl ligand, the catalyst systems described herein may be used to modulate these polymer properties and afford more catalyst options for polymer product differentiations as well as polymerization process and configuration flexibility. [0008] Embodiments of this disclosure include catalysts systems. The catalyst system includes a procatalyst having a structure according to Formula (I): 86026-WO-PCT/DOW 86026 WO [0009] In Formula (I), M is a metal selected from titanium, zirconium, and hafnium, the metal having a formal oxidation state of +2, +3, or +4. n is 1 or 2. Each X is a monodentate or bidentate ligand independently selected from unsaturated (C2−C30)hydrocarbon, unsaturated (C2−C30)heterohydrocarbon, (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, halogen, ^N(RX)2, and −(CH2)wSi(RX)3, where w is 1 to 10 and each RX is independently selected from (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, and (C3–C30)heteroaryl. [0010] In Formula (I), RY is (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, or (C3–C30)heteroaryl. R1 is (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C6–C30)aryl, or (C3–C30)heteroaryl. Each of R2 and R3 is independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, −ORC, −Si(RC)3, −Ge(RC)3, halogen, and –H, wherein R2 and R3 are optionally covalently linked to form an aromatic or non-aromatic ring. Each RC is independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, and –H. Each of R8–12 is independently selected from (C1–C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, −Si(RC)3, −Ge(RC)3, and −H, wherein optionally, any of R8-12 are covalently connected to form one or more aromatic or non-aromatic ring or multi-ring structures. [0011] Embodiments of this disclosure include polymerization processes, particularly methods of making ethylene-based polymers. The methods of making include polymerizing, via solution phase polymerization in a reactor, ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of the catalyst system including a procatalyst having a structure according to Formula (I). 86026-WO-PCT/DOW 86026 WO DETAILED DESCRIPTION [0012] Specific embodiments of catalyst systems will now be described. It should be understood that the catalyst systems of this disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure. Rather, embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art. [0013] Common abbreviations are listed below: [0014] R, Q, M, X and n: as defined above; Me : methyl; Et : ethyl; Ph : phenyl; Bn: benzyl; Cy : cyclohexyl; Mes : mesityl (2,4,6-trimethylphenyl); i-Pr : iso-propyl; nBu : n-butyl; t-Bu : tert-butyl; t-Oct : tert-octyl (2,4,4-trimethylpentan-2-yl); Tf : trifluoromethane sulfonate; : Et2O : diethyl ether; THF : tetrahydrofuran; DCM or CH2Cl2 : dichloromethane; DMSO : dimethyl sulfoxide; EtOH : ethanol; DIW : deionized water; C6D6 : deuterated benzene or benzene-d6 : CDCl3 : deuterated chloroform; Na2SO4 : sodium sulfate; MgSO4 : magnesium sulfate; HCl : hydrogen chloride; BINAP : 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl; K2CO3: potassium carbonate; K3PO4 : tripotassium phosphate; NH4Cl : ammonium chloride; Pd(Ph3)4 : tetrakis(triphenylphosphine)palladium(0); Pd2(dba)3 : tris(dibenzylideneacetone)dipalladium(0); HfBn4 : hafnium(IV) tetrabenzyl; ZrCl4 : zirconium(IV) chloride; ZrBn4 : zirconium(IV) tetrabenzyl; IMesNH : 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; tBuNH : 1,3-di(tert- butyl)imidazol-2-ylidene; Cy3PNH: tricyclohexyl-phosphinimine; CpZrBn3 : cyclopentadienylzirconium(IV) tribenzyl; nBuCpZrBn3 : n-butylcyclopentadienylzirconium(IV) tribenzyl; MeCpZrBn3 : methylcyclopentadienylzirconium(IV) tribenzyl; MeCpZrCl3 : methylcyclopentadienylzirconium(IV) trichloride; ; IPrNZrBn3 : 1,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidenezirconium(IV) tribenzyl; IPrNHfBn3 : 1,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidenehafnium(IV) tribenzyl; tricyclohexyl- phosphinimideziconium(IV) tribenzyl; Cy3PNHfBn3 : tricyclohexyl-phosphinimidehafnium(IV) tribenzyl; N2 : nitrogen gas; PhMe: toluene; PPR : parallel pressure reactor; MAO : methylaluminoxane; MMAO : modified methylaluminoxane; TEA : triethylaluminum; GC : gas chromatography; LC : liquid chromatography; RIBS-2: bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine; NMR : nuclear magnetic resonance; MS: mass spectrometry; PTFE : Polytetrafluoroethylene; mmol : millimoles; mL : milliliters; M : molar; min or mins: minutes; h or hrs : hours; d: days; rpm: revolution per minute. 86026-WO-PCT/DOW 86026 WO [0015] The term “spectator ligand” refers to a ligand that occupies a coordination site on the metal center of a metal–ligand complex and influences the reactivity of the metal center, but remains bound and does not de-coordinate from the metal center during the course of polymerization. Spectator ligands are also referred to as “ancillary ligands” and are generally less basic or less easily protonated than ligands that de-coordinate from the metal center during polymerization. [0016] In this disclosure, a “heteroleptic” metal–ligand complex refers to a metal–ligand complex bearing a spectator ligand and one or more additional ligands that are the same or different from one another. At minimum, a heteroleptic complex contains both a spectator ligand and a ligand that participates in chemical reactions carried out by the metal–ligand complex, such as olefin polymerization, by de-coordinating from the metal center of the metal–ligand complex. [0017] 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 RC can be identical or different, without dependency on the identity of any other group also appearing before the term. [0018] 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. [0019] 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 (C1^C30)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 RS substituted 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 “(C1^C50)alkyl substituted with exactly one group RS, where RS is phenyl (−C6H5)” may contain from 7 to 56 carbon atoms. Thus, in general when a chemical group defined using the “(Cx^Cy)” parenthetical is substituted by one or more carbon atom-containing substituents RS, the minimum and maximum total number of carbon atoms of the chemical group is determined 86026-WO-PCT/DOW 86026 WO 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. [0020] 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. [0021] The term “(C1^C30)hydrocarbyl” means a hydrocarbon radical of from 1 to 30 carbon atoms and the term “(C1^C30)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 RS or unsubstituted. Examples of (C1^C30)hydrocarbyl are unsubstituted or substituted (C1^C30)alkyl, (C3^C30)cycloalkyl, (C3^C20)cycloalkyl-(C1^C10)alkylene, (C6^C30)aryl, or (C6^C20)aryl-(C1-C10)alkylene (such as benzyl (−CH2−C6H5)). Examples of (C1^C50)hydrocarbyl are unsubstituted or substituted (C1^C50)alkyl, (C3^C50)cycloalkyl, (C3^C20)cycloalkyl-(C1^C20)alkylene, (C6^C40)aryl, or (C6^C20)aryl-(C1-C20)alkylene (such as benzyl (−CH2−C6H5)). [0022] The term “(C1^C50)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 (C1^C50)alkyl are unsubstituted (C1^C20)alkyl; unsubstituted (C1^C10)alkyl; unsubstituted (C1^C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1- dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Examples of substituted 86026-WO-PCT/DOW 86026 WO (C1^C40)alkyl are substituted (C1^C20)alkyl (such as benzyl (−CH2−C6H5)), substituted (C1^C10)alkyl, trifluoromethyl, and [C45]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^C40)alkyl substituted by one RS, which is a (C1^C5)alkyl, respectively. Each (C1^C5)alkyl may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl. [0023] The term “(C6^C40)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 non-fused and aromatic or non- aromatic. Examples of unsubstituted (C6^C40)aryl include: unsubstituted (C6^C20)aryl, unsubstituted (C6^C18)aryl; 2-(C1^C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (C6^C40)aryl include: substituted (C1^C20)aryl; substituted (C6^C18)aryl; 2,4-bis([C20]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9- one-l-yl. [0024] The term “(C3^C50)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^C40)cycloalkyl are unsubstituted (C3^C20)cycloalkyl, unsubstituted (C3^C10)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3^C40)cycloalkyl are substituted (C3^C20)cycloalkyl, substituted (C3^C10)cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl. [0025] Examples of (C1^C50)hydrocarbylene include unsubstituted or substituted (C6^C50)arylene, (C3^C50)cycloalkylene, and (C1^C50)alkylene (e.g., (C1^C20)alkylene). The 86026-WO-PCT/DOW 86026 WO 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 α,ω-diradical, and others a 1,2-diradical. The α,ω-diradical is a diradical that has maximum carbon backbone spacing between the radical carbons. Some examples of (C2^C20)alkylene α,ω-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 (C6^C50)arylene α,ω-diradicals include phenyl-1,4-diyl, napthalen-2,6-diyl, or napthalen-3,7-diyl. [0026] The term “(C1^C50)alkylene” 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 (C1^C50)alkylene are unsubstituted (C1^C20)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 (C1^C50)alkylene are substituted (C1^C20)alkylene, ^CF2^, ^C(O)^, and ^(CH2)14C(CH3)2(CH2)5^ (i.e., a 6,6-dimethyl substituted normal-1,20-eicosylene). Since as mentioned previously two RS may be taken together to form a (C1^C18)alkylene, examples of substituted (C1^C50)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. [0027] The term “(C3^C50)cycloalkylene” means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more RS. Other cycloalkylene groups (e.g., (Cx^Cy)cycloalkylene) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more RS. [0028] 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 RC and each RP is unsubstituted (C1^C18)hydrocarbyl or ^H, and where each RN is unsubstituted (C1−C18)hydrocarbyl. The term 86026-WO-PCT/DOW 86026 WO “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 “(C1−C50)heterohydrocarbyl” means a heterohydrocarbon radical of from 1 to 50 carbon atoms, and the term “(C1−C50)heterohydrocarbylene” means a heterohydrocarbon diradical of from 1 to 50 carbon atoms. The heterohydrocarbon of the (C1−C50)heterohydrocarbyl or the (C1−C50)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 (C1^C50)heterohydrocarbyl and (C1^C50)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. [0029] The (C1^C50)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (C1^C50)heterohydrocarbyl include (C1^C50)heteroalkyl, (C1^C50)hydrocarbyl-O^, (C1^C50)hydrocarbyl-S^, (C1^C50)hydrocarbyl-S(O)^, (C1^C50)hydrocarbyl-S(O)2^, (C1^C50)hydrocarbyl-Si(RC)2^, (Cl^C50)hydrocarbyl-N(RN)^, (Cl^C50)hydrocarbyl-P(RP)^, (C2^C50)heterocycloalkyl, (C2^C19)heterocycloalkyl- (C1^C20)alkylene, (C3^C20)cycloalkyl-(C1^C19)heteroalkylene, (C2^C19)heterocycloalkyl- (C1^C20)heteroalkylene, (C1^C50)heteroaryl, (C1^C19)heteroaryl-(C1^C20)alkylene, (C6^C20)aryl- (C1^C19)heteroalkylene, or (C1^C19)heteroaryl-(C1^C20)heteroalkylene. [0030] The (C1^C30)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (C1^C30)heterohydrocarbyl include (C1^C30)heteroalkyl, (C1^C30)hydrocarbyl-O^, (C1^C30)hydrocarbyl-S^, (C1^C30)hydrocarbyl-S(O)^, (C1^C30)hydrocarbyl-S(O)2^, (C1^C30)hydrocarbyl-Si(RC)2^, (Cl^C30)hydrocarbyl-N(RN)^, (Cl^C30)hydrocarbyl-P(RP)^, (C2^C30)heterocycloalkyl, (C2^C20)heterocycloalkyl- 86026-WO-PCT/DOW 86026 WO (C1^C10)alkylene, (C3^C20)cycloalkyl-(C1^C10)heteroalkylene, (C2^C20)heterocycloalkyl- (C1^C10)heteroalkylene, (C1^C30)heteroaryl, (C1^C20)heteroaryl-(C1^C10)alkylene, (C6^C20)aryl- (C1^C10)heteroalkylene, or (C1^C20)heteroaryl-(C1^C10)heteroalkylene. [0031] The term “(C3^C50)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^C12)heteroaryl) are defined in an analogous manner as having from x to y carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or substituted by one or more than one RS. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered ring or a 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1, 2, or 3; and each heteroatom may be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol-1-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- 1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-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 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An Example of the fused 5,6,6-ring system is 1H-benzo[f] indol-1-yl. An Example of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An Example of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An Example of the fused 6,6,6-ring system is acrydin-9-yl. 86026-WO-PCT/DOW 86026 WO [0032] The term “(C1−C50)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 “(C1−C50)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. [0033] Examples of unsubstituted (C2^C40)heterocycloalkyl include unsubstituted (C2^C20)heterocycloalkyl, unsubstituted (C2^C10)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. [0034] 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−). [0035] 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 carbon–carbon 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. [0036] Embodiments of the catalysts systems described herein include a procatalyst having a structure according to Formula (I): 86026-WO-PCT/DOW 86026 WO [0037] In Formula (I), M is a metal selected from titanium, zirconium, and hafnium, the metal having a formal oxidation state of +2, +3, or +4. n is 1 or 2. Each X is a monodentate or bidentate ligand independently selected from unsaturated (C2−C30)hydrocarbon, unsaturated (C2−C30)heterohydrocarbon, (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, halogen, ^N(RX)2, and −(CH2)wSi(RX)3, where w is 1 to 10 and each RX is independently selected from (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, and (C3–C30)heteroaryl. Formula (I) is overall charge neutral. [0038] Without intent to be bound by theory, it is believed that the presence of both the cyclopentadienyl ligand and the 2-amino-imidazole ligand on the same metal center of the catalysts described herein may be advantageous for achieving improved catalyst activity and tunable polymer properties, relative to homoleptic 2-amino-imidazole complexes wherein the ligands bonded to the metal center, other than the 2-amino-imidazole ligand, are the same (e.g., three benzyl ligands). Further, it has been unexpectedly found that embodiments of the heteroleptic 2-amino-imidazole complexes described herein have increased catalyst activities relative to their homoleptic analogs while also producing polymers with low comonomer incorporation and low weight-average molecular weight, the combination of which is believed to be favorable for polymer processability. Moreover, it is believed that the Group IV heteroleptic complexes described herein having a coordination sphere comprising both the 2-amino-imidazole ligand and the cyclopentadienyl ligand may demonstrate high activity at elevated temperatures (e.g., up to at least 150 °C) while also achieving ultra-high ethylene selectivity (e.g., resulting in ≥ 99.5 mol% units derived from ethylene for the produced polymer). Therefore, the combination of these ligands on the same metal center creates efficient and highly ethylene-selective catalysts whose molecular weight capability can be further adjusted through synthetic modification on the 86026-WO-PCT/DOW 86026 WO overall catalyst framework. The catalyst systems described herein thus afford more catalyst options for polymer product differentiations as well as polymerization process and configuration flexibility. [0039] In Formula (I), RY is (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, or (C3–C30)heteroaryl. R1 is (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C6–C30)aryl, or (C3–C30)heteroaryl. Each of R2 and R3 is independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, −ORC, −Si(RC)3, −Ge(RC)3, halogen, and –H, wherein R2 and R3 are optionally covalently linked to form an aromatic or non-aromatic ring. Each RC is independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, and –H. Each of R8–12 is independently selected from (C1–C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, −Si(RC)3, −Ge(RC)3, and −H, wherein optionally, any of R8-12 are covalently connected to form one or more aromatic or non-aromatic ring or multi-ring structures. [0040] In one or more embodiments, in Formula (I), each X is independently selected from (C1−C10)alkyl, (C6−C20)aryl, and halogen, and R1 is (C1−C30)alkyl or (C6−C30)aryl. In some embodiments of this disclosure, in Formula (I), n is 2. In other embodiments, n is 1. In other embodiments, n is 1or 2. In one or more embodiments, each X is independently selected from the group consisting of methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro. [0041] In one or more embodiments, RY is (C1−C8)alkyl. In embodiments, RY is methyl, ethyl, 1-propyl, 2-propyl, n-butyl, tert-butyl, 2-methylpropyl (iso-butyl), n-butyl, n-hexyl, cyclohexyl, n-octyl, tert-octyl, or benzyl. [0042] In one or more embodiments, in Formula (I), R1 is (C6−C30)aryl. In one or more embodiments, R1 is unsubstituted phenyl, substituted phenyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted naphthyl, or substituted naphthyl. In various embodiments, R1 is unsubstituted phenyl or substituted phenyl. In various embodiments, R1 is 2-methylphenyl, 2-(iso-propyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,6-di(iso-propyl)phenyl, 2,4,6-tri(iso-propyl)phenyl, 3,5-di(tert-butyl)phenyl, 3,5-diphenylphenyl, or 2,3,5,6-tetrafluorophenyl, or 2-(1-naphthyl)phenyl. [0043] In one or more embodiments, R1 is (C1−C12)alkyl, (C1−C12)cycloalkyl, trimethylsilyl methyl, benzyl, or 1-adamantyl. 86026-WO-PCT/DOW 86026 WO [0044] In one or more embodiments, the (C1−C30)hydrocarbyl of R2 and R3 may be a (C6−C30)aryl and the (C1−C30)heterohydrocarbyl of R2 and R3 may be a (C3−C30)heteroaryl. [0045] In some embodiments, R2 and R3 are covalently linked to form an aromatic ring, and the procatalyst has a structure according to Formula (II): [0046] In one or more embodiments, in Formula (II), each R1, RY, R8-12, Q, X, M, and n are defined as in Formula (I) and each of R4, R5, R6, and R7 is independently (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, (C6–C40)aryl, (C3–C40)heteroaryl, halogen, or −H. In one or more embodiments, each of R5 , R6, and R7 is −H. [0047] In one or more embodiments, R4 is (C6−C40)aryl or (C3−C40)heteroaryl. In some embodiments, R4 is (C6−C40)aryl or (C3−C40)heteroaryl, and each of R5, R6, and R7 is –H. [0048] In one or more embodiments, R4 is phenyl, 2,4,6-tri(iso-propyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 3,5-di(tert-butyl)phenyl, unsubstituted naphthyl, substituted naphthyl, unsubstituted carbozolyl, or substituted carbozolyl. In one or more embodiments, R1 is unsubstituted phenyl or substituted phenyl. In some embodiments, R4 is phenyl, 2,4,6-tri(iso-propyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 3,5-di(tert- butyl)phenyl, unsubstituted naphthyl, substituted naphthyl, unsubstituted carbozolyl, or substituted carbozolyl, and each of R5, R6, and R7 is –H. [0049] In some embodiments of this disclosure, in Formulas (I) and (II), n is 2. In other embodiments, n is 1. [0050] In various embodiments, R1 is (C6−C30)aryl; R4 is phenyl, 2,4,6-tri(iso-propyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 3,5-di(tert-butyl)phenyl, unsubstituted naphthyl, 86026-WO-PCT/DOW 86026 WO substituted naphthyl, unsubstituted carbozolyl, or substituted carbozolyl; and each of R5, R6, and R7 is −H. [0051] In some embodiments, each of R8-11 is −H and R12 is (C1−C10)alkyl, (C6^C20)aryl, (C1−C20)heterohydrocarbyl, ^Si(RC)3, or ^Ge(RC)3. In embodiments, each of R8–R11 is –H and R12 is (C1−C10)alkyl or (C6^C20)aryl. [0052] In the procatalyst according to Formula (I) or Formula (II), each X bonds with M through a covalent bond, a dative bond, or an ionic bond. In some embodiments, each X is identical. The procatalyst may have 6 or fewer metal^ligand bonds and may be overall charge-neutral or may have a positive charge associated with the metal center. [0053] In embodiments where X is a monodentate ligand, the monodentate ligand may be a monoanionic ligand. In embodiments where X is a bidentate ligand, the bidentate ligand may be 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. Each monoanionic ligand may independently be hydride, (C1^C20)hydrocarbyl carbanion, (C1^C20)heterohydrocarbyl carbanion, halide, nitrate, carbonate, phosphate, sulfate, HC(O)O−, HC(O)N(H)−, (C1^C20)hydrocarbylC(O)O−, (C1^C20)hydrocarbylC(O)N((C1^C20)hydrocarbyl)−, (C1^C20)hydrocarbylC(O)N(H)−, RKRLB-, RKRLN−, RKO−, RKS−, RKRLP−, or RMRKRLSi−, where each RK, RL, and RM independently is hydrogen, (C1^C20)hydrocarbyl, or (C1^C20)heterohydrocarbyl, or RK and RL are taken together to form a (C2^C20)hydrocarbylene or (C1^C20)heterohydrocarbylene and RM is as defined above. In one embodiment, each dianionic ligand may independently be carbonate, oxalate (i.e., −O2CC(O)O−, (C2^C40)hydrocarbylene dicarbanion, (C1-C40)heterohydrocarbylene dicarbanion, phosphate, or sulfate. [0054] In other embodiments, at least one monodentate ligand X, independently from any other ligands X, may be a neutral ligand. In specific embodiments, the neutral ligand is a neutral Lewis base group such as RJNRKRL, RKORL, RKSRL, or RJPRKRL, where each RJ independently is hydrogen, [(C1^C10)hydrocarbyl]3Si(C1^C10)hydrocarbyl, (C1^C20)hydrocarbyl, [(C1^C10)hydrocarbyl]3Si, or (C1^C20)heterohydrocarbyl and each RK and RL independently is as previously defined. 86026-WO-PCT/DOW 86026 WO [0055] Additionally, each X can be a monodentate ligand that, independently from any other ligands X, is a halogen, unsubstituted (C1^C20)hydrocarbyl, unsubstituted (C1^C20)hydrocarbylC(O)O–, or RKRLN−, wherein each of RK and RL independently is an unsubstituted(C1^C20)hydrocarbyl. In some embodiments, each monodentate ligand X is a chlorine atom, (C1^C10)hydrocarbyl (e.g., (C1^C6)alkyl or benzyl), unsubstituted (C1^C10)hydrocarbylC(O)O–, or RKRLN−, wherein each of RK and RL independently is an unsubstituted (C1^C10)hydrocarbyl. In one or more embodiments of Formula (I) and (II), X is benzyl, chloro, −CH2SiMe3, or phenyl. [0056] In further embodiments, each X is independently selected from (C1−C10)alkyl, (C6^C20)aryl, and a halogen. [0057] In further embodiments, each X is selected from methyl; ethyl; 1-propyl; 2-propyl; 1- butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chloro. In some embodiments, each X is the same. In other embodiments, the two X ligands are different from each other. In the embodiments in which the two X ligands are different from one another, X is a different one of methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2,-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chloro. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-silapropane- l,3-diyl or 1,3-butadiene. [0058] In further embodiments, each X is independently selected from methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro. [0059] In some embodiments, any or all of the chemical groups (e.g., X, R1−R3, and R8–R12) of the procatalyst of Formula (I) may be unsubstituted. In other embodiments, none, any, or all of the chemical groups X, R1−R3, and R8−R12 of the procatalyst of Formula (I) may be substituted with one or more than one RS. When two or more than two RS are bonded to a same chemical group of the procatalyst of Formula (I), the individual RS of 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 X, R1−R3, and R8−R12 may be persubstituted with RS. In the chemical groups that are persubstituted with RS, the individual RS may all be the same or may be independently chosen. [0060] In some embodiments, any or all of the chemical groups (e.g., X, R1, R4−R7, and R8–R12) of the procatalyst of Formula (II) may be unsubstituted. In other embodiments, none, any, 86026-WO-PCT/DOW 86026 WO or all of the chemical groups X, R1, R4−R7, and R8–R12 of the procatalyst of Formula (II) may be substituted with one or more than one RS. When two or more than two RS are bonded to a same chemical group of the procatalyst of Formula (II), the individual RS of 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 X, R1, R4−R7, and R8–R12 may be persubstituted with RS. In the chemical groups that are persubstituted with RS, the individual RS may all be the same or may be independently chosen. [0061] In illustrative embodiments, the catalyst systems include a procatalyst according to Formula (I) or (II) having the structure of any one of Procatalysts 1–3 below: Procatalyst 3 86026-WO-PCT/DOW 86026 WO [0062] Embodiments of this disclosure include polymerization processes. The polymerization processes include polymerizing, via solution phase polymerization in a reactor, ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of a catalyst system comprising a procatalyst according to Formula (I). Co-catalyst Component [0063] In embodiments of the present disclosure, the catalyst system may include a co-catalyst component. The catalyst system comprising a procatalyst of Formula (I) may be rendered catalytically active by any technique known in the art for activating metal-based catalysts of olefin polymerization reactions. For example, the procatalyst according Formula (I) may be rendered catalytically active by contacting the procatalyst to, or combining the procatalyst with, one or more activating co-catalysts (also referred to herein as an “activators”). Additionally, the procatalyst according for Formula (I) includes both a procatalyst form, which is neutral, and a catalytic form, which may be positively charged due to the loss of a monoanionic ligand, such as benzyl or phenyl. Suitable activating co-catalysts for use herein include, without limitation: alkyl aluminums; boron-based Bronsted or Lewis acids; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions); and combinations thereof. A suitable activating technique is bulk electrolysis. Combinations of one or more of the foregoing activating co-catalysts and techniques are also contemplated. The term “alkyl aluminum” means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane. [0064] Lewis acid activating co-catalysts include Group 13 metal compounds containing (C1^C20)hydrocarbyl substituents as described herein. In some embodiments, Group 13 metal compounds are tri((C1^C20)hydrocarbyl)-substituted-aluminum or tri((C1^C20)hydrocarbyl)- boron compounds. In other embodiments, Group 13 metal compounds are tri(hydrocarbyl)- substituted-aluminum, tri((C1^C20)hydrocarbyl)-boron compounds, tri((C1^C10)alkyl)aluminum, tri((C6^C18)aryl)boron compounds, and halogenated (including perhalogenated) derivatives thereof. In further embodiments, Group 13 metal compounds are tris(fluoro-substituted 86026-WO-PCT/DOW 86026 WO phenyl)boranes, tris(pentafluorophenyl)borane. In some embodiments, the activating co-catalyst is a tris((C1^C20)hydrocarbyl borate (e.g. trityl tetrafluoroborate) or a tri((C1^C20)hydrocarbyl)ammonium tetra((C1^C20)hydrocarbyl)borane (e.g. bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term “ammonium” means a nitrogen cation that is a ((C1^C20)hydrocarbyl)4N+ a ((C1^C20)hydrocarbyl)3N(H)+, a ((C1^C20)hydrocarbyl)2N(H)2 +, (C1^C20)hydrocarbylN(H)3 +, or N(H)4 +, wherein each (C1^C20)hydrocarbyl, when two or more are present, may be the same or different. [0065] Combinations of neutral Lewis acid activating co-catalysts include mixtures comprising a combination of a tri((C1^C4)alkyl)aluminum and a halogenated tri((C6^C18)aryl)boron compound, especially a tris(pentafluorophenyl)borane. Other embodiments are combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane. Ratios of numbers of moles of (metal–ligand complex): (tris(pentafluoro-phenylborane): (alumoxane) [e.g., (Group 4 metal–ligand complex) :(tris(pentafluoro-phenylborane):(alumoxane)] are from 1:1:1 to 1:10:30, in other embodiments, from 1:1:1.5 to 1:5:10. [0066] Exemplary suitable activating co-catalysts include, but are not limited to, methylaluminoxane (MAO), modified methyl aluminoxane (MMAO), triethylaluminum (TEA), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1−) amine (RIBS-2), and combinations thereof. [0067] In particular embodiments, the activating co-catalyst comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof. [0068] In particular embodiments, the activating co-catalyst comprises unsubstituted ammonium borate, a mono-substituted ammonium borate, a bi-substituted ammonium borate, a tri-substituted ammonium borate, or a tetra-substituted ammonium borate. [0069] In particular embodiments, the activating co-catalyst comprises bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1−) amine (RIBS-2). 86026-WO-PCT/DOW 86026 WO [0070] In some embodiments, more than one of the foregoing activating co-catalysts may be used in combination with each other. A specific example of an activating co-catalyst combination is a mixture of a tri((C1^C4)hydrocarbyl)aluminum, tri((C1–C4)hydrocarbyl)borane, or an ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of total number of moles of one or more procatalysts of Formula (I) to total number of moles of one or more of the activating co-catalysts is from 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5,000, in some other embodiments, at least 1: 1,000; and 10:1 or less, and in some other embodiments, 1:1 or less. When an alumoxane alone is used as the activating co-catalyst, preferably the number of moles of the alumoxane that are employed is at least 100 times the number of moles of the procatalyst of Formula (I). When tris(pentafluorophenyl)borane alone is used as the activating co-catalyst, in some other embodiments, the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of one or more procatalysts of Formula (I) from 0.5: 1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activating co-catalysts are generally employed in approximately mole quantities equal to the total mole quantities of one or more procatalysts of Formula (I). [0071] In some embodiments, when more than one of the foregoing co-catalyst components is used in combination, one or more of the co-catalyst components may function as a scavenger. The purpose of the scavenger is to react with any water or other impurities present in the system that might otherwise react with the catalyst leading to reduced efficiency. In embodiments, the catalyst systems described herein may include an activator or both an activator and a scavenger. [0072] In some embodiments, the co-catalyst component includes an activator comprising unsubstituted ammonium borate, a mono-substituted ammonium borate, a bi-substituted ammonium borate, a tri-substituted ammonium borate, or a tetra-substituted ammonium borate, and a scavenger comprising methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof. [0073] In some embodiments, the co-catalyst component includes an activator comprising bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine (RIBS-2), and a scavenger comprising methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof. 86026-WO-PCT/DOW 86026 WO Supported Catalyst Systems [0074] In embodiments, the catalyst systems described herein may be supported catalyst systems wherein the procatalysts described herein, the co-catalyst component, or both, may be disposed on one or more support materials. For example, the procatalysts may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more support materials. The procatalysts, the co-catalyst component, or both, may be combined with one or more support materials using one of the support methods well known in the art or as described below. As used in the present disclosure, the procatalysts, the co-catalyst component, or both, may be in a supported form, for example, when deposited on, contacted with, or incorporated within, adsorbed or absorbed in, or on, one or more support materials. [0075] In other embodiments the co-catalyst component and the support material are contacted together in an inert hydrocarbon liquid to give a suspension of a supported co-catalyst component in the inert hydrocarbon liquid, then the suspension is contacted with the procatalyst to give a suspension of the supported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed to give the supported catalyst system. [0076] The removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may include a step of decanting some of the inert hydrocarbon liquid from the suspension. In some embodiments the decanting method comprises pouring off excess inert hydrocarbon liquid from the suspension to give a concentrated suspension of the supported catalyst system. [0077] The removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may comprise a step of drying the supported catalyst system. The drying step may comprise a spray-drying method. [0078] A “support,” which may also be referred to as a “carrier,” refers to any support material, including a porous support material, such as talc, inorganic oxides, and inorganic chlorides. Other support materials include resinous support materials, e.g., polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof. 86026-WO-PCT/DOW 86026 WO [0079] Suitable support materials, such as inorganic oxides, include oxides of metals of Group 2, 3, 4, 5, 13 or 14 of the IUPAC periodic table. In embodiments, support materials include silica, which may or may not be dehydrated, fumed silica, alumina (e.g., as described in International Patent Application No.1999/060033), silica-alumina, and mixtures of these. The fumed silica may be hydrophilic (untreated), alternatively hydrophobic (treated). In embodiments, the support material is hydrophobic fumed silica, which may be prepared by treating an untreated fumed silica with a treating agent, such as dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane. In some embodiments, support materials include magnesia, titania, zirconia, magnesium chloride (e.g., as described in U.S. Patent No. 5,965,477), montmorillonite (e.g., as described in European Patent No. 0511665), phyllosilicate, zeolites, talc, clays (e.g., as described in U.S. Patent No. 6,034,187), and mixtures of these. In other embodiments, combinations of these support materials may be used, such as, for example, silica-chromium, silica-alumina, silica-titania, and combinations of these. Additional support materials may also include those porous acrylic polymers described in European Patent No.0767184. Other support materials may also include nanocomposites described in International Patent Application No. 1999/047598; aerogels described in International Patent Application No. 1999/048605; spherulites described in U.S. Patent No.5,972,510; and polymeric beads described in International Patent Application No. 1999/050311. An example of a support material is fumed silica available under the trade name CABOSIL TS- 610, or other TS- or TG-series supports, available from Cabot Corporation. Fumed silica is typically a silica with particles 7 to 30 nanometers in size that have been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped. [0080] In embodiments, the support material has a surface area of from 10 square meters per gram (m2/g) to 700 m2/g, a pore volume of from 0.1 cubic meters per gram (cm3/g) to 4.0 cm3/g, and an average particle size of from 5 microns (µm) to 500 µm. In some embodiments, the support material has a surface area of from 50 m2/g to 500 m2/g, a pore volume of from 0.5 cm3/g to 3.5 cm3/g, and an average particle size of from 10 µm to 200 µm. In other embodiments, the support material may have a surface area of from 100 m2/g to 400 m2/g, a pore volume from 0.8 cm3/g to 3.0 cm3/g, and an average particle size of from 5 µm to 100 µm. The average pore size of the support material is typically from 10 Angstroms (Å) to 1,000 Å, such as from 50 Å to 500 Å or from 75 Å to 350 Å. 86026-WO-PCT/DOW 86026 WO [0081] The support material may comprise silica, alternatively amorphous silica (not quartz), alternatively a high surface area amorphous silica, e.g., from 500 to 1000 m2/g. Such silicas are commercially available from several sources including the Davison Chemical Division of W.R. Grace and Company, e.g., Davison 952 and Davison 955 products, and PQ Corporation, e.g., ES70 product. The silica may be in the form of spherical particles, which may be obtained by a spray-drying process. Alternatively, MS3050 product is a silica from PQ Corporation that is not spray-dried. As procured, these silicas are not calcined (i.e., not dehydrated). Silica that is calcined prior to purchase may also be used as the support material. [0082] In some embodiments the solid support is a hydrophobic fumed silica. The hydrophobic fumed silica is made by contacting an untreated fumed silica, having surfaces containing silicon- bonded hydroxyl groups (Si-OH groups), with a hydrophobing agent, described later. In some embodiments the hydrophobing agent is a silicon-based hydrophobing agent, containing on average per molecule one or more functional groups reactive with a Si-OH group, to give the hydrophobic fumed silica. The silicon-based hydrophobing agent may be selected from (CH3)2SiCl2, a polydimethylsiloxane, hexamethyldisilazane (HMDZ), and a (C1–C10)alkyl-Si((C1–C10)alkoxy)3 (e.g., an octyltrialkoxysilane such as octyltriethoxysilane, i.e., CH3(CH2)7Si(OCH2CH3)3). In some embodiments the silicon-based hydrophobing agent is dimethyldichlorosilane, i.e., (CH3)2SiCl2. In some embodiments the support material is a dimethyldichlorosilane-treated fumed silica, such as that sold as product TS-610 from Cabot Corporation. [0083] The support material may be uncalcined or calcined. The calcined support material is made prior to being contacted with a procatalyst, co-catalyst component, and/or hydrophobing agent, by heating the support material in air to give a calcined support material. The calcining comprises heating the support material at a peak temperature from 350 °C to 850 °C, alternatively from 400 °C to 800 °C, alternatively from 400 °C to 700 °C, alternatively from 500 °C to 650 °C and for a time period from 2 to 24 hours, alternatively from 4 to 16 hours, alternatively from 8 to 12 hours, alternatively from 1 to 4 hours, thereby making the calcined support material. If the support material has not been heated in this way it is an uncalcined support material. 86026-WO-PCT/DOW 86026 WO Polymerization Processes [0084] As noted above, embodiments of this disclosure include polymerization processes. The polymerization processes include polymerizing, via solution phase polymerization in a reactor, ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of a catalyst system comprising a procatalyst 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. [0085] 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, wherein ethylene and optionally one or more ^-olefins are polymerized in the presence of the catalyst system, as described herein, and optionally one or more co-catalysts. In another embodiment, the ethylene-based polymer may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and optionally one or more ^-olefins are polymerized in the presence of the catalyst system in this disclosure. The catalyst system, as described herein, can be used in the first reactor, or second reactor, optionally in combination with one or more other catalysts. In one embodiment, the ethylene based-polymer may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and optionally one or more ^-olefins are polymerized in the presence of the catalyst system, as described herein, in both reactors. [0086] 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 optionally one or more α-olefins are polymerized in the presence of the catalyst system, as described within this disclosure, and optionally one or more co-catalyst components, as described in the preceding paragraphs. 86026-WO-PCT/DOW 86026 WO [0087] In embodiments, methods for producing the ethylene-based polymer may include feeding hydrogen into the reactor during solution phase polymerization. [0088] The ethylene-based polymers may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene based-polymers may contain any amounts of additives. The ethylene-based polymers may compromise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the ethylene-based polymers and the one or more additives. The ethylene-based polymers may further comprise fillers, which may include, but are not limited to, organic or inorganic fillers. The ethylene based-polymers may contain from about 0 to about 20 weight percent fillers such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the combined weight of the ethylene-based polymers and all additives or fillers. The ethylene-based polymers may further be blended with one or more polymers to form a blend. [0089] In some embodiments, a method of making an ethylene-based polymer may include polymerizing ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer in the presence of a catalyst system, wherein the catalyst system incorporates at least procatalyst of Formula (I). Polyolefins [0090] The catalytic systems described in the preceding paragraphs are utilized in the polymerization of olefin-based polymers. While the catalytic systems of this disclosure are utilized in the polymerization of ethylene, it should be understood that such catalytic systems may be utilized in the polymerization of other olefins, such as propylene. In some embodiments, there is only a single type of olefin or 1-alkene (α-olefin) in the polymerization scheme, creating a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomers typically have no more than 20 carbon atoms. For example, the α-olefin comonomers may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-l-pentene. For example, the one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or in the alternative, from the group consisting of 1-hexene and 1-octene. 86026-WO-PCT/DOW 86026 WO [0091] The ethylene-based polymers, for example homopolymers and/or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins, may comprise from at least 50 percent by weight monomer units derived from ethylene, based on a total weight of the ethylene-based polymer. All individual values and subranges encompassed by “from at least 50 weight percent” are disclosed herein as separate embodiments; for example, the ethylene-based polymers, homopolymers and/or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins may comprise at least 60 weight percent monomer units derived from ethylene; at least 70 weight percent monomer units derived from ethylene; at least 80 weight percent monomer units derived from ethylene; or from 50 to 100 weight percent monomer units derived from ethylene; or from 80 to 100 weight percent units derived from ethylene. Common forms of ethylene-based polymer known in the art include: Low Density Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-site catalyzed Linear Low Density Polyethylene, including both linear and substantially linear low density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE). [0092] In some embodiments, the ethylene-based polymers may comprise at least 90 mole percent (mol%) units derived from ethylene. All individual values and subranges from at least 90 mol% are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymers may comprise at least 93 mol% units derived from ethylene, at least 95 mol% units derived from ethylene, at least 96 mol% units derived from ethylene, at least 97 mol% units derived from ethylene, at least 98 mol% units derived from ethylene, at least 99 mol% units derived from ethylene, at least 99.5 mol% units derived from ethylene, or at least 99.9 mol% units derived from ethylene. In embodiments, the ethylene-based polymers may comprise from 90 to 100 mol% units derived from ethylene, from 95 to 100 mol% units derived from ethylene, from 97 to 100 mol% units derived from ethylene, from 98 to 100 mol% units derived from ethylene, from 99 to 100 mol% units derived from ethylene, from 99.5 to 100 mol% units derived from ethylene, or from 99.95 to 100 mol% units derived from ethylene. In embodiments, the ethylene-based polymers may comprise from 90 to 99.95 mol% units derived from ethylene, from 95 to 99.95 mol% units derived from ethylene, from 97 to 99.95 mol% units derived from ethylene, from 98 to 99.95 mol% units derived from ethylene, from 99 to 99.95 mol% units derived from ethylene, or from 99.5 to 99.95 mol% units derived from ethylene, or from 99.9 to 99.95 mol% units derived from ethylene. 86026-WO-PCT/DOW 86026 WO [0093] In some embodiments, the ethylene-based polymers may comprise at most 50 mol% units derived from at least one α-olefin comonomer. In further embodiments, the ethylene-based polymers may comprise at most 25 mol% units derived from at least one α-olefin comonomer, at most 10 mol% units derived from at least one α-olefin comonomer, at most 8 mol% units derived from at least one α-olefin comonomer, at most 5 mol% units derived from at least one α-olefin comonomer, at most 4 mol% units derived from at least one α-olefin comonomer, at most 3.6 mol% units derived from at least one α-olefin comonomer, at most 3 mol% units derived from at least one α-olefin comonomer, at most 2.5 mol% units derived from at least one α-olefin comonomer, at most 2.1 mol% units derived from at least one α-olefin comonomer, at most 2 mol% units derived from at least one α-olefin comonomer, at most 1.8 mol% units derived from at least one α-olefin comonomer, at most 1.6 mol% units derived from at least one α-olefin comonomer, at most 1.4 mol% units derived from at least one α-olefin comonomer, at most 1.2 mol% units derived from at least one α-olefin comonomer, at most 1.0 mol% units derived from at least one α-olefin comonomer, at most 0.8 mol% units derived from at least one α-olefin comonomer, at most 0.6 mol% units derived from at least one α-olefin comonomer, at most 0.5 mol% units derived from at least one α-olefin comonomer, at most 0.4 mol% units derived from at least one α-olefin comonomer, at most 0.3 mol% units derived from at least one α-olefin comonomer, at most 0.2 mol% units derived from at least one α-olefin comonomer, or at most 0.1 mol% units derived from at least one α-olefin comonomer. [0094] In some embodiments, the ethylene-based polymers may comprise from 0.05 mol% to 4 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 3.6 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 3 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 2.5 mol% units derived from at least one α- olefin comonomer, from 0.05 mol% to 2.1 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 2 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 1.8 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 1.6 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 1.4 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 1.2 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 1.0 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 0.8 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 0.6 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 0.5 mol% units derived from at least one α-olefin comonomer, from 86026-WO-PCT/DOW 86026 WO 0.05 mol% to 0.4 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 0.3 mol% units derived from at least one α-olefin comonomer, from 0.05 mol% to 0.2 mol% units derived from at least one α-olefin comonomer, or from 0.05 mol% to 0.1 mol% units derived from at least one α-olefin comonomer. In some embodiments, the additional ^-olefin comonomer include 1-butene, 1-hexene, or 1-octene. In some embodiments, the additional ^-olefin comonomer includes 1-octene. [0095] In some embodiments, the ethylene-based polymer polymerized in the presence of a catalyst system described herein including procatalyst of Formula (I) may have a density according to ASTM D792 (incorporated herein by reference in its entirety) from 0.850 g/cm3 to 0.970 g/cm3, 0.870 g/cm3 to 0.950 g/cm3, from 0.880 g/cm3 to 0.920 g/cm3, from 0.880 g/cm3 to 0.910 g/cm3, 0.900 g/cm3 to 0.950 g/cm3, 0.920 g/cm3 to 0.950 g/cm3, from 0.950 g/cm3 to 0.970 g/cm3, or from 0.880 g/cm3 to 0.900 g/cm3, for example. [0096] In some embodiments, the ethylene-based polymer polymerized in the presence of a catalyst system described herein including procatalyst of Formula (I) has a melt flow ratio (I10/I2) from 5 to 15, in which melt index I2 is measured according to ASTM D1238 (incorporated herein by reference in its entirety) at 190 °C and 2.16 kg load, and melt index I10 is measured according to ASTM D1238 at 190 °C and 10 kg load. In other embodiments the melt flow ratio (I10/I2) is from 5 to 10, and in others, the melt flow ratio is from 5 to 9. [0097] In some embodiments, the ethylene-based polymer polymerized in the presence of a catalyst system described herein has a weight-average molecular weight of less than 450,000 g/mol, less than 425,000 g/mol, less than 400,000 g/mol, less than 375,000 g/mol, less than 350,000 g/mol, less than 275,000 g/mol, less than 225,000 g/mol, less than 200,000 g/mol, less than 175,000 g/mol, less than 150,000 g/mol, less than 125,000 g/mol, less than 100,000 g/mol, less than 75,000 g/mol, or even less than 50,000 g/mol. In embodiments, the polymer resulting from the catalyst system that includes the procatalyst of Formula (I) has a weight-average molecular weight from 300 g/mol to 450,000 g/mol, from 300 g/mol to 425,000 g/mol, from 300 g/mol to 400,000 g/mol, from 300 g/mol to 375,000 g/mol, from 300 g/mol to 350,000 g/mol, from 300 g/mol to 325,000 g/mol, from 300 g/mol to 300,000 g/mol, from 300 g/mol to 275,000 g/mol, from 300 g/mol to 250,000 g/mol, from 300 g/mol to 225,000 g/mol, from 300 g/mol to 200,000 g/mol, from 300 g/mol to 175,000 g/mol, from 86026-WO-PCT/DOW 86026 WO 300 g/mol to 150,000 g/mol, from 300 g/mol to 125,000 g/mol, from 300 g/mol to 100,000 g/mol, , or from 300 g/mol to 70,000 g/mol. [0098] 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/Mn with Mw being a weight-average molecular weight and Mn being 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. [0099] 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. [0100] One or more features of the present disclosure are illustrated in view of the examples as follows: EXAMPLES [0101] All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. All commercial chemicals were used without further purification. Anhydrous toluene, hexanes, tetrahydrofuran, and diethyl ether were purified via passage through activated alumina and, in some cases, Q-5 reactant (also known as Q5). Solvents used for experiments performed in a nitrogen-filled glovebox were further dried by storage over activated 3Å molecular sieves. Trichloride metal precursors CpZrCl3, nBuCpZrCl3, and MeCpZrCl3 were purchased from either Strem Chemicals or Sigma Aldrich, or they were prepared according to the procedure in WO2016/168448. Glassware for moisture-sensitive reactions was dried in an oven overnight prior to use. NMR spectra were recorded on Bruker Avance NEO 500 and Bruker Avance 400 spectrometers. LC-MS analyses were performed using a Waters e2695 Separations Module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separations were performed on an XBridge C183.5 μm 2.1x50 mm column using a 5:95 to 100:0 acetonitrile to water gradient with 0.1% formic acid as the 86026-WO-PCT/DOW 86026 WO ionizing agent. HRMS analyses were performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8μm 2.1x50 mm column coupled with an Agilent 6230 TOF Mass Spectrometer with electrospray ionization. [0102] 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 for NMR data are reported in ppm downfield from internal tetramethylsilane (TMS, δ scale) using residual protons in the deuterated solvent as references.13C NMR data were determined with decoupling, and the chemical shifts are reported downfield from tetramethylsilane (TMS, δ scale) in ppm versus the using residual carbons in the deuterated solvent as references. [0103] Examples 1 to 18 are synthetic procedures for ligand intermediates, ligands, monoanionic spectator ligands, heteroleptic metal precursors, and isolated procatalysts. In Example 19, the results of PPR Screening Experiments and batch reactor polymerization tests are tabulated and discussed. Synthesis of Precursor Compounds for 2-Amino-Imidazole Ligands Example 1 3-fluoro-2',4',6'-trimethyl-2-nitro-1,1'-biphenyl [0104] In a fumehood, 1-bromo-3-fluoro-2-nitrobenzene (10.0 g, 45.45 mmol, 1 equiv), mesityl boronic acid (11.18 g, 68.18 mmol, 1.5 equiv), and toluene (250 mL) were added to a 500 mL 3-neck round bottom flask along with a magnetic stir bar. Separately, K3PO4 (28.94 g, 136.4 mmol, 3 equiv) and water (10 mL) were combined in a flask to allow the base to fully dissolve. This solution was then added to the 3-neck flask also. The entire mixture was allowed to stir at ambient temperature while sparging with a stream of nitrogen for 1 h. After this time, solid Pd(PPh3)4 (5.25 g, 4.55 mmol, 0.1 equiv) was added to the reaction flask under a gentle stream of 86026-WO-PCT/DOW 86026 WO nitrogen. After addition of the catalyst, a water-cooled reflux condenser was put in place and the bright yellow heterogeneous reaction mixture was stirred at 100 °C under nitrogen for 20 h. The next day, the reaction mixture was cooled to ambient temperature, diluted with water (200 mL), and transferred to a separatory funnel. The mixture was extracted with ethyl acetate (3 x 250 mL), and the combined organics were then dried with magnesium sulfate and filtered. The filtrate was concentrated on vacuum and then purified by column chromatography using a 0 to 30% ethyl acetate in hexanes solvent gradient. The fractions shown by GC-MS to contain the desired product were combined. The solvent was removed in vacuo to afford the product that was further purified through recrystallization from hexanes. Yield: 10.2 g, 86.5 %. [0105] 1H NMR (500 MHz, CDCl3) δ 7.58 – 7.50 (m, 1H), 7.32 – 7.23 (overlapping with CDCl3 solvent, 1H), 7.03 (dd, J = 7.7, 1.1 Hz, 1H), 6.90 (s, 2H), 2.30 (s, 3H), 2.00 (s, 6H). Example 2 N-isopropyl-2',4',6'-trimethyl-2-nitro-[1,1'-biphenyl]-3-amine [0106] In a fumehood, 3-fluoro-2',4',6'-trimethyl-2-nitro-1,1'-biphenyl (2.60 g, 10.0 mmol, 1 equiv) was combined with DMSO (20 mL) and a magnetic stir bar in a 50 mL round bottom flask. The mixture was allowed to stir gently while K2CO3 (4.16 g, 30.1 mmol, 3 equiv) and iso- propylamine (6.03 mL, 70.2 mmol, 7 equiv) were added. The reaction mixture was then heated to 80 °C and stirred for 18 h. After cooling to ambient temperature, the mixture was diluted with water (10 mL), transferred to a separatory funnel, and extracted with ethyl acetate (3 x 100 mL). The combined organic extracts were then dried with MgSO4, filtered, and concentrated to a bright red-orange oil. The oil was taken up in Et2O, washed with DIW and brine, dried over MgSO4, and filtered. The filtrate was concentrated to a bright red-orange oil that then solidified upon standing. The solids were analyzed by NMR, which confirmed the target product identity and purity. Yield: 2.5 g, 83.6 %. 86026-WO-PCT/DOW 86026 WO [0107] 1H NMR (500 MHz, CDCl3) δ 7.36 (t, J = 7.9 Hz, 1H), 6.89 (s, 2H), 6.83 (d, J = 8.6 Hz, 1H), 6.38 (dt, J = 7.2, 1.1 Hz, 1H), 6.12 (d, J = 7.1 Hz, 1H), 3.78 (hept, J = 6.4 Hz, 1H), 2.31 (s, 3H), 2.02 (s, 6H), 1.31 (dd, J = 6.3, 1.1 Hz, 6H). Example 3 1-isopropyl-4-mesityl-1H-benzo[d]imidazole [0108] In a fumehood, N-isopropyl-2',4',6'-trimethyl-2-nitro-[1,1'-biphenyl]-3-amine (1.00 g, 3.35 mmol, 1 equiv) was combined with THF (14 mL), EtOH (14 mL), iron powder (0.94 g, 16.8 mmol, 5 equiv), and a magnetic stir bar at ambient temperature in a 100 mL round bottom flask. To this gently stirring mixture, a solution of NH4Cl (0.269 g, 5.03 mmol, 1.5 equiv) in DIW (4.5 mL) was added. The reaction was then put under nitrogen with a water-cooled reflux condenser in place and then heated to 95 °C for 4 h. After this time, the heterogeneous black reaction mixture was cooled to ambient temperature, diluted with ethyl acetate (50 mL), and filtered through Celite®. The Celite® pad was additionally washed with ethyl acetate (2 x 10 mL). The filtrate was then combined with saturated NH4Cl (aq) and extracted with ethyl acetate (3 x 50 mL). The combined extracts were washed with DIW (2 x 50 mL) and then with brine (50 mL). The organics were then dried over MgSO4, filtered, and concentrated by rotary evaporation. The material was then transferred to a 60 mL glass vial with septa cap and combined with triethyl orthoformate (10 mL) and a magnetic stir bar. The reaction mixture was then heated at reflux for 3 h. After cooling, the reaction mixture was then diluted with DCM (20 mL), combined with silica gel, and concentrated by rotary evaporation. The material was then purified by column chromatography using a 0 to 30 % gradient of ethyl acetate in hexanes. The target benzimidazole was isolated by combining the fractions whose GC-MS indicated product and concentrating by rotary evaporation. Yield: 0.610 g, 65.4 %. 86026-WO-PCT/DOW 86026 WO [0109] 1H NMR (400 MHz, CDCl3) δ 7.92 (s, 1H), 7.41 (dt, J = 8.2, 1.1 Hz, 1H), 7.37 – 7.29 (m, 1H), 7.06 (dt, J = 7.1, 1.1 Hz, 1H), 6.97 (s, 2H), 4.66 (hept, J = 6.7 Hz, 1H), 2.33 (s, 3H), 1.97 (s, 6H), 1.66 (dd, J = 6.8, 1.1 Hz, 6H). Example 4 2-bromo-1-isopropyl-4-mesityl-1H-benzo[d]imidazole [0110] In a fumehood, 1-isopropyl-4-mesityl-1H-benzo[d]imidazole (1.61 g, 5.78 mmol, 1 equiv) was combined with THF (20 mL) and a magnetic stir bar in a 60 mL glass vial with a septa cap. Once dissolved, N-bromosuccinimide (1.08 g, 6.07 mmol, 1.05 equiv) was added at ambient temperature. The reaction mixture was then heated at reflux for 4 h. After this time, the reaction mixture was cooled to ambient temperature, the volatiles were evaporated, and the resulting residue was purified by column chromatography using a 0 to 30 % ethyl acetate in hexanes gradient. The combined fractions were concentrated by rotary evaporation, affording the desired product. Yield: 1.90 g, 92.0 %. [0111] 1H NMR (500 MHz, CDCl3) δ 7.53 (dd, J = 8.3, 1.0 Hz, 1H), 7.30 (t, J = 7.8 Hz, 1H), 7.04 (d, J = 7.4 Hz, 1H), 6.95 (s, 2H), 4.98 (hept, J = 7.0 Hz, 1H), 2.33 (s, 3H), 1.97 (s, 6H), 1.72 (d, J = 6.9 Hz, 6H). Synthesis of 2-Amino-Imidazole Ligands 86026-WO-PCT/DOW 86026 WO Example 5 Ligand 1 (L-1) - N-(2,6-dimethylphenyl)-1-isopropyl-4-mesityl-1H-benzo[d]imidazol-2-amine [0112] In a nitrogen filled glovebox, 2-bromo-1-isopropyl-4-mesityl-1H-benzo[d]imidazole (0.215 g, 0.60 mmol, 1 equiv) was combined toluene (6 mL) and a magnetic stir bar in a 60 mL glass vial with a septa cap at ambient temperature. To this stirring solution, Pd2(dba)3 (0.055 g, 0.06 mmol, 0.1 equiv), BINAP (0.037 g, 0.06 mmol, 0.1 equiv), and sodium tert-butoxide (0.128 g, 1.34 mmol, 2.22 equiv) were then added followed by 2,6-dimethylaniline (0.126 mL, 0.1.02 mmol, 1.7 equiv). The reaction mixture was capped and then heated at 100 °C for 3 h. The resulting dark purple-brown heterogeneous reaction mixture was allowed to cool to ambient temperature, removed from the glovebox, diluted with ethyl acetate (30 mL), and filtered through a silica plug. The plug was additionally washed with ethyl acetate (30 mL) and the filtrate and washes were combined. Volatiles were removed in vacuo and the crude material was purified by column chromatography using a 0 to 10 % gradient of ethyl acetate in hexanes. The target product was isolated as a yellow oil that solidified upon standing. Yield: 0.180 g, 75.2 %. [0113] 1H NMR (500 MHz, DMSO-d6) δ 7.78 (s, 1H), 7.39 (d, J = 7.9 Hz, 1H), 7.05 – 6.91 (m, 4H), 6.79 (s, 2H), 6.62 (d, J = 7.4 Hz, 1H), 4.90 (hept, J = 6.9 Hz, 1H), 2.19 (s, 3H), 2.10 (s, 6H), 1.83 (s, 6H), 1.62 (d, J = 6.8 Hz, 6H). Example 6 Ligand 2 (L-2) - N-benzyl-1-isopropyl-4-mesityl-1H-benzo[d]imidazol-2-amine [0114] Ligand 2 was prepared in accordance with Example 52 of WO 2020/263790 A1. 86026-WO-PCT/DOW 86026 WO [0115] 1H NMR (400 MHz, CDCl3) δ 7.38 - 7.27 (m, 5H), 7.23 (dd, J= 7.9, 1.1 Hz, 1H), 7.06 (t, J= 7.7 Hz, 1H), 6.97 (s, 2H), 6.88 (dd, J= 7.5, 1.0 Hz, 1H), 4.60 (s, 2H), 4.41 (hept, J = 7.0 Hz, 1H), 4.19 (s, 1H), 2.35 (s, 3H), 2.06 (s, 6H), 1.62 (d, J= 6.9 Hz, 6H). Example 7 Ligand 3 (L-3) - N-cyclohexyl-1-isopropyl-4-mesityl-1H-benzo[d]imidazol-2-amine [0116] Ligand 3 was prepared in accordance with Example 54 of WO 2020/263790 A1. [0117] 1H NMR (400 MHz, CDCl3) δ 7.22 (d, J = 8.0 Hz, 1H), 7.04 (t, J= 7.7 Hz, 1H), 6.97 (s, 2H), 6.86 (d, J= 7.4 Hz, 1H), 4.53 - 4.33 (m, 1H), 3.78 (m, 2H), 2.36 (s, 3H), 2.06 (s, 6H), 1.77- 1.67 (m, 4H), 1.64 (d, J= 6.9 Hz, 6H), 1.40 (q, J= 14.5, 13.3 Hz, 2H), 1.24- 1.14 (m, 2H). Example 8 Ligand 4 (L-4) - 1-isopropyl-4-mesityl-N-pentyl-1H-benzo[d]imidazol-2-amine [0118] Ligand 4 was prepared in accordance with Example 55 of WO 2020/263790 A1. [0119] 1H NMR (400 MHz, CDCl3) δ 7.22 (dd, J= 7.9, 1.1 Hz, 1H), 7.05 (t, J= 7.7 Hz, 1H), 6.97 (s, 2H), 6.86 (dd, J= 7.5, 1.1 Hz, 1H), 4.42 (p, J= 7.0 Hz, 1H), 3.86 (t, J= 5.7 Hz, 1H), 3.41(q, J= 6.6 Hz, 2H), 2.36 (s, 3H), 2.07 (d, J= 1.4 Hz, 6H), 1.64 (m, 8H), 1.35 (q, J= 3.7 Hz, 4H), 0.95 - 0.86 (m, 3H). 86026-WO-PCT/DOW 86026 WO Synthesis of Heteroleptic Metal Precursors Example 9 Tricyclohexyl-phosphinimine (Cy3PNH) [0120] In a glovebox, tricyclohexylphosphine (0.750, 2.67 mmol, 1 equiv) was added to a 40 mL glass vial along with a magnetic stir bar and toluene (6 mL) at ambient temperature. Trimethylsilyl azide (0.531 mL, 4.01 mmol, 1.5 equiv) was added dropwise at ambient temperature while maintaining gentle stirring. After the addition was complete, the reaction was heated to 85 °C for 18 h. The reaction mixture was cooled to ambient temperature, filtered, and concentrated to dryness. The resulting residue was triturated with hexanes (2 x 2 mL) and the volatiles were removed in vacuo, affording a solid. The material was redissolved in toluene (2 mL), and an excess of anhydrous methanol (2 mL) was added. The resulting mixture was stirred for 12 h at 40 °C. The mixture was concentrated to a solid. The solid was triturated with hexanes (3 x 2 mL), washed with hexanes (2 x 2 mL), and dried in vacuo, affording a nearly colorless solid. Yield: 0.61 g, 77.2%. [0121] 1H NMR (400 MHz, C6D6) δ 2.01 – 1.80 (m, 6H), 1.80 – 1.48 (m, 12H), 1.48 – 1.23 (m, 6H), 1.21 – 0.99 (m, 9H), 0.23 (s, 1H). 13C NMR (101 MHz, C6D6) δ.13C NMR (101 MHz, c6d6) δ 128.30, 128.29, 128.06, 128.05, 127.82, 127.81, 36.40, 35.85, 27.51, 27.40, 27.34, 27.23, 27.20, 26.87, 26.72, 26.70. 31P NMR (162 MHz, C6D6) δ 36.57. 86026-WO-PCT/DOW 86026 WO Example 10 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPrNH) [0122] In a glovebox, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (1.00 g, 2.57 mmol, 1.0 equiv) was added to a 100 mL round bottom flask along with a magnetic stir bar and toluene (10 mL) at ambient temperature. Trimethylsilyl azide (1.03 mL, 7.72 mmol, 3.0 equiv) was added dropwise at ambient temperature while maintaining gentle stirring. After the addition was complete, the reaction was heated to 120 °C with a reflux condenser in place for 14 h. The volatiles were removed by vacuum and the resulting colorless, waxy solid was dissolved in toluene (5 mL) and methanol (2 mL) was added. The mixture was stirred for 2 h at ambient temperature. The volatiles were removed under vacuum and the resulting residue was suspended in hexanes and stored in the refrigerator overnight. The insoluble material was collected on a filter and washed with additional portions of cold hexanes. Yield: 0.814 g, 78.4%. [0123] 1H NMR (400 MHz, C6D6): δ 7.26 (m, 4 H), 7.14 (s, 2 H), 5.84 (s, 2 H), 4.21 (s, 1H), 3.12 (sept, J = 6.9 Hz, 4 H), 1.34 (d, J = 6.9 Hz, 12 H), 1.19 (d, J = 6.9 Hz, 12 H). 13C NMR (101 MHz, C6D6): δ 154.2, 148.3, 133.1, 130.0, 124.5, 114.0, 29.1, 24.0, 24.0. Example 11 Cy3PNZrBn3 [0124] In a nitrogen filled glovebox, a vial was charged with ZrBn4 (0.500 g, 1.097 mmol, 1 equiv) and Cy3P=NH (0.324 g, 1.097 mmol, 1 equiv) and toluene (5 mL). The mixture was stirred overnight, concentrated, and triturated with hexanes to afford a pale yellow solid. 86026-WO-PCT/DOW 86026 WO [0125] 1H NMR (400 MHz, C6D6) δ 7.21 – 7.12 (m, 6H), 6.95 (t, J = 7.4 Hz, 3H), 6.83 (d, J = 6.8 Hz, 6H), 1.96 (s, 6H), 1.79 (d, J = 13.6 Hz, 6H), 1.75 – 1.66 (m, 6H), 1.64 – 1.52 (m, 6H), 1.29 (q, J = 12.5 Hz, 6H), 1.09 (d, J = 7.9 Hz, 9H). 13C NMR (126 MHz, C6D6) δ 144.16, 129.76, 126.66, 121.50, 59.31, 36.04, 35.58, 26.88, 26.78, 26.71, 26.69, 26.14.31P NMR (202 MHz, C6D6) δ 16.62. Example 12 IPrNZrBn3 [0126] In a glovebox, a 20 mL vial was charged with ZrBn4 (0.500 g, 0.875 mmol, 1 equiv), 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPrNH) (0.442 g, 0.875 mmol, 1 equiv), and toluene (5mL). The mixture was stirred for 18 h at room temperature, followed by filtration concentration under vacuum. The resulting material was triturated with hexanes (5 mL), collected by filtration, washed with hexanes, and dried under vacuum, affording a yellow solid. Yield: 0.488 g, 58%. [0127] 1H NMR (500 MHz, C6D6) δ 7.25 (dd, J = 8.4, 7.1 Hz, 2H), 7.16 (d, J = 7.5 Hz, 4H), 7.03 (t, J = 7.7 Hz, 6H), 6.92 – 6.84 (m, 3H), 6.36 – 6.19 (m, 6H), 5.92 (s, 2H), 3.14 (hept, J = 6.9 Hz, 4H), 1.41 (d, J = 6.9 Hz, 12H), 1.36 (s, 6H), 1.15 (d, J = 6.9 Hz, 12H). 13C NMR (126 MHz, C6D6) δ 147.42, 143.01, 142.58, 134.10, 130.23, 130.10, 127.32, 124.46, 121.99, 114.39, 60.27, 29.20, 24.50, 23.65. Example 13 CpZrBn3 86026-WO-PCT/DOW 86026 WO [0128] In a nitrogen filled glovebox, CpZrCl3 (1.15 g, 4.37 mmol, 1 equiv), a magnetic stir bar, and toluene (10 mL) were combined in a 50 mL glass jar and stored at −25 °C for 60 min. Separately, a 1.0 M solution of BnMgCl in diethyl ether (13.8 mL, 13.88 mmol, 3.15 equiv) was added to a 20 mL glass vial and also stored at −25 °C for 60 min. After this cooling time, the Grignard solution was added dropwise to the gray/brown suspension of Zr precursor in toluene while stirring vigorously. The suspension gradually turned vibrant yellow/orange as the addition was carried out. The reaction mixture was then allowed to warm to ambient temperature and left to continue stirring vigorously at ambient temperature for 60 min. The resulting bright yellow suspension was then filtered through a disposable PTFE filter and the filter cake was washed with toluene (10 mL). The golden yellow filtrate was concentrated under vacuum, affording a bright yellow solid that was triturated with hexanes (2 × 10 mL) and washed with hexanes (2 × 20 mL). The bright yellow solid was then extracted into in toluene (2 x 20 mL) and concentrated to 10 mL prior to storage at −25 °C for 48 h. Yellow crystals were collected by separating the mother liquor and washing the crystals with hexanes (1.5 mL). The crystals were dried under vacuum. Yield: 1.20 g, 63.9 %. [0129] 1H NMR (400 MHz, C6D6) δ 7.11 – 7.04 (m, 6H), 6.99 – 6.92 (m, 3H), 6.50 – 6.44 (m, 6H), 5.60 (s, 5H), 1.49 (s, 6H). 13C NMR (101 MHz, C6D6) δ 143.5, 130.1, 127.6, 123.6, 111.9, 65.7. Example 14 nBuCpZrBn3 [0130] In a nitrogen filled glovebox, nBuCpZrCl3 (1.03 g, 3.23 mmol, 1 equiv), a magnetic stir bar, and toluene (30 mL) were combined in a 50 mL glass jar and stored at −25 °C for 60 min. Separately, a 1.0 M solution of BnMgCl in diethyl ether (10.0 mL, 10.0 mmol, 3.1 equiv) was added to a 20 mL vial with toluene (5 mL) and also stored at −25 °C for 60 min. After this cooling time, the Grignard solution was added dropwise to the pale orange solution of Zr precursor while stirring. The pale orange reaction mixture was allowed to warm to ambient temperature and left to continue stirring vigorously at ambient temperature for 24 h. The mixture was filtered through 86026-WO-PCT/DOW 86026 WO Celite® and then concentrated under vacuum, affording an amber oil. The oil was then triturated with hexanes (2 × 10 mL), extracted into pentane (30 mL), and filtered. All the volatiles were removed in vacuo, affording a pale amber oil. Yield: 1.22 g, 77.7 %. [0131] 1H NMR (400 MHz, C6D6) δ 7.09 (t, J = 7.6 Hz, 6H), 6.99 – 6.92 (m, 3H), 6.55 (dd, J = 8.2, 1.4 Hz, 6H), 5.60 (t, J = 2.7 Hz, 2H), 5.43 (t, J = 2.7 Hz, 2H), 2.23 – 2.15 (m, 2H), 1.59 (s, 6H), 1.46 – 1.34 (m, 2H), 1.30 – 1.17 (m, 2H), 0.86 (t, J = 7.3 Hz, 3H).13C NMR (101 MHz, C6D6) δ 144.0, 130.0, 127.7, 123.5, 111.9, 111.6, 66.4, 33.8, 29.8, 22.7, 14.1. Example 14 MeCpZrBn3 [0132] In a nitrogen filled glovebox, MeCpZrCl3 (0.500 g, 1.81 mmol, 1 equiv) was combined with toluene (12 mL) and a stir bar in a 20 mL glass vial. The resulting mixture was stored at −25 °C for 60 min. Separately, a 1.0 M solution of BnMgCl in diethyl ether (5.69 mL, 5.69 mmol, 3.15 equiv) was added to a 20 mL glass vial and also stored at −25 °C for 60 min, upon which the Grignard solution was added dropwise to the stirring mixture of Zr precursor. Over the course of the addition of BnMgCl the appearance of the reaction mixture changed to a yellow suspension. The reaction mixture was allowed to warm to ambient temperature and continue stirring for an additional 4 h. The volatiles were removed in vacuo and the resulting yellow residue was triturated with hexanes (3 x 5 mL) and dried under vacuum. The material was then extracted into toluene (15 mL), filtered, and concentrated. The golden-yellow filtrate was stored at −25 °C overnight leading to the formation of golden-yellow crystals. The crystals were collected by decanting the mother liquor, rinsing the crystals with a minimal amount of hexanes, and drying in vacuo. Only a single crop of crystals was collected. Yield: 0.355 g, 44.3%. [0133] 1H NMR (400 MHz, C6D6) δ 7.08 (dd, J = 8.3, 7.0 Hz, 6H), 6.99 – 6.86 (m, 3H), 6.52 (dd, J = 8.2, 1.3 Hz, 6H), 5.53 (t, J = 2.7 Hz, 2H), 5.38 (t, J = 2.6 Hz, 2H), 1.79 (s, 3H), 1.54 (s, 6H). 13C NMR (101 MHz, C6D6) δ 143.9, 130.0, 127.7, 124.3, 123.5, 112.7, 111.6, 66.2, 14.8. 86026-WO-PCT/DOW 86026 WO Synthesis of Inventive Procatalysts Example 15 Procatalyst 1 [0134] In a nitrogen filled glovebox, nBuCpZrBn3 (0.050 g, 0.10 mmol, 1 equiv) was combined with C6D6 (0.5 mL) and a magnetic stir bar at ambient temperature, affording an amber-colored solution. Separately, N-(2,6-dimethylphenyl)-1-isopropyl-4-mesityl-1H-benzo[d]imidazol-2- amine (L-1) (0.041 g, 0. 10 mmol, 1 equiv) was combined with C6D6 (0.5 mL), affording a colorless solution. The colorless solution of benzimidazole was then added dropwise to the amber solution of nBuCpZrBn3 while gently stirring at ambient temperature, causing a color change to yellow-orange. Additional C6D6 (0.2 mL) was used to ensure quantitative transfer of all the ligand material into the reaction vial. The reaction mixture was then allowed to stir at ambient temperature overnight in the glovebox for 18 h. The next day, the reaction mixture was concentrated under reduced pressure and then triturated with hexanes (2 x 2 mL). The target complex was obtained as a pale yellow-orange solid. Yield: 0.068 g, 83.5 %. [0135] 1H NMR (400 MHz, C6D6) 1H NMR (400 MHz, C6D6) δ 7.19 – 7.12 (resonances overlapping with NMR solvent, 4H), 7.04 – 7.00 (overlapping resonances, 2H), 7.00 – 6.92 (overlapping resonances, 2H), 6.91 – 6.81 (overlapping resonances, 6H), 6.80 – 6.72 (m, 4H), 5.68 (t, J = 2.7 Hz, 2H), 5.48 (t, J = 2.7 Hz, 2H), 3.72 (hept, J = 6.9 Hz, 1H), 2.41 (d, J = 10.2 Hz, 2H), 2.31 (d, J = 10.2 Hz, 2H), 2.28 (s, 3H), 2.26 (s, 6H), 2.00 (t, J = 7.5 Hz, 2H), 1.88 (s, 6H), 1.23 – 1.07 (m, 4H), 1.02 (d, J = 7.0 Hz, 6H), 0.75 (t, J = 7.1 Hz, 3H).13C NMR (126 MHz, C6D6) δ 159.71, 149.99, 145.99, 139.54, 137.59, 137.14, 137.03, 133.99, 132.21, 131.08, 129.33, 128.98, 128.73, 126.23, 125.52, 125.09, 121.14, 120.10, 116.23, 112.94, 110.12, 70.68, 46.40, 34.02, 28.73, 22.64, 21.54, 21.31, 20.41, 19.07, 13.97. 86026-WO-PCT/DOW 86026 WO Example 17 Procatalyst 2 [0136] In a nitrogen filled glovebox, MeCpZrBn3 (0.050 g, 0.11 mmol, 1 equiv) was combined with C6D6 (0.5 mL) and a magnetic stir bar at ambient temperature, affording an amber-colored solution. Separately, N-(2,6-dimethylphenyl)-1-isopropyl-4-mesityl-1H-benzo[d]imidazol-2- amine (L-1) (0.045 g, 0. 11 mmol, 1 equiv) was combined with C6D6 (0.5 mL), affording a colorless solution. The colorless solution of benzimidazole was then added dropwise to the amber solution of MeCpZrBn3 while gently stirring at ambient temperature, causing a color change to yellow-orange. Additional C6D6 (0.2 mL) was used to ensure quantitative transfer of all the ligand material into the reaction vial. The reaction mixture was then allowed to stir at ambient temperature overnight in the glovebox for 18 h. The next day, the reaction mixture was concentrated under reduced pressure and then triturated with hexanes (2 x 2 mL). The target complex was obtained as a pale yellow-orange solid. Yield: 0.071 g, 84.1 %. [0137] 1H NMR (400 MHz, C6D6) δ 7.16 – 7.11 (overlapping with NMR solvent, 4H), 7.04 – 6.99 (overlapping resonances, 2H), 6.94 (dd, J = 5.4, 3.4 Hz, 1H), 6.90 – 6.82 (overlapping resonances, 7H), 6.76 – 6.70 (m, 4H), 5.60 (t, J = 2.7 Hz, 2H), 5.42 (t, J = 2.7 Hz, 2H), 3.70 (hept, J = 7.0 Hz, 1H), 2.39 (d, J = 10.2 Hz, 2H), 2.29 (d, J = 10.5 Hz, 2H), 2.27 (s, 3H), 2.25 (s, 6H), 1.85 (s, 6H), 1.62 (s, 3H), 1.01 (d, J = 7.0 Hz, 6H). 13C NMR (126 MHz, C6D6) δ 159.68, 149.87, 145.95, 139.53, 137.58, 137.14, 137.03, 133.96, 132.20, 129.33, 128.98, 128.72, 128.49, 126.25, 125.58, 125.54, 125.10, 121.15, 120.09, 116.99, 112.97, 110.12, 70.42, 46.39, 21.54, 21.45, 21.31, 20.41, 19.05, 13.88. 86026-WO-PCT/DOW 86026 WO [0138] In a nitrogen filled glovebox, CpZrBn3 (0.050 g, 0.12 mmol, 1 equiv) was combined with C6D6 (0.5 mL) and a magnetic stir bar at ambient temperature, affording an amber-colored solution. Separately, N-(2,6-dimethylphenyl)-1-isopropyl-4-mesityl-1H-benzo[d]imidazol-2- amine (L-1) (0.046 g, 0. 12 mmol, 1 equiv) was combined with C6D6 (0.5 mL), affording a colorless solution. The colorless solution of benzimidazole was then added dropwise to the amber solution of CpZrBn3 while gently stirring at ambient temperature, causing a color change to yellow-orange. Additional C6D6 (0.2 mL) was used to ensure quantitative transfer of all the ligand material into the reaction vial. The reaction mixture was then allowed to stir at ambient temperature overnight in the glovebox for 18 h. The next day, the reaction mixture was concentrated under reduced pressure and then triturated with hexanes (2 x 2 mL). The target complex was obtained as a pale yellow-orange solid. Yield: 0.072 g, 84.2 %. [0139] 1H NMR (400 MHz, C6D6) δ 7.18 – 7.09 (overlapping with NMR solvent, 4H), 7.02 – 6.98 (m, 2H), 6.97 – 6.93 (m, 1H), 6.88 – 6.82 (overlapping resonances, 7H), 6.72 – 6.66 (m, 4H), 5.54 (s, 5H), 3.67 (hept, J = 7.0 Hz, 1H), 2.35 (d, J = 10.2 Hz, 2H), 2.29 (s, 3H), 2.27 (d, J = 10.3 Hz, 2H), 2.24 (s, 6H), 1.80 (s, 6H), 0.98 (d, J = 7.0 Hz, 6H).13C NMR (101 MHz, C6D6) δ 159.70, 149.84, 146.10, 139.43, 137.90, 137.62, 137.21, 136.91, 133.83, 132.12, 130.08, 129.34, 128.96, 128.71, 128.58, 125.88, 125.70, 125.52, 125.05, 121.13, 120.13, 114.82, 111.94, 110.13, 70.53, 46.39, 21.52, 21.43, 21.31, 20.39, 19.00. 86026-WO-PCT/DOW 86026 WO Example 19 Polymerization Reactions General Procedure for PPR Screening Experiments [0140] In situ heteroleptic precatalyst screening is performed in a high throughput parallel pressure reactor (PPR) system. The PPR system is composed of an array of 48 single-cell (6 x 8 matrix) reactors in an inert-atmosphere glovebox. Each cell is equipped with a glass insert with an internal working liquid volume of approximately 5 mL. Each cell has independent controls for pressure, and the liquid in the cell is continuously stirred at 800 rpm. Catalyst solutions, unless otherwise noted, are prepared in toluene. All liquids (for example, solvent, 1-octene, and catalyst solutions) are added to the single-cell reactors via robotic syringes. Gaseous reagents (for example, ethylene, CO) are added to the single-cell reactors via a gas injection port. Prior to each run, the reactors are heated to 80 °C, purged with ethylene, and vented. [0141] The reactors are heated to the run temperature and pressured to the appropriate psig with ethylene. A portion of Isopar-E is added to the reactors. Toluene solutions of reagents are added in the following order: (1) 1-octene with 500 nmol of scavenger MMAO-3A; (2) 1.5 equivalents activator (RIBS-II); and (3) catalyst (20 or 100 nmol). [0142] Each liquid addition is chased with a small amount of Isopar E so that after the final addition a total reaction volume of 5 mL is reached. Upon addition of the catalyst, the PPR software begins monitoring the pressure of each cell. The desired pressure (within approximately 2–6 psig) is maintained by the supplemental addition of ethylene gas by opening the valve at the set point minus 1 psi and closing it when the pressure reached 2 psi higher. All drops in pressure are cumulatively recorded as “Uptake” or “Conversion” of the ethylene for the duration of the run or until the uptake or conversion requested value is reached, whichever occurs first. Each reaction is then quenched by addition of 10% carbon monoxide in argon for 4 minutes at 40–50 psi higher than the reactor pressure. The shorter the “Quench Time,” the more active the catalyst. Catalyst Activity was quantified by Equation 1: (Equation 1) [0143] To prevent formation of too much polymer in any given cell, the reaction is quenched upon reaching a predetermined uptake level (50 psig). After the reaction mixtures are quenched, 86026-WO-PCT/DOW 86026 WO cooled to 70 °C, vented, and purged for 5 minutes with nitrogen to remove carbon monoxide, the tubes are removed. The polymer samples are then dried in a centrifugal evaporator at 70 °C for 12 hours, weighed to determine polymer yield, and submitted for IR (1-octene incorporation) and GPC (molecular weight) analysis. Batch Reactor Polymerization Procedure [0144] 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. 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 reactant. The ethylene is passed through two columns, the first containing A204 alumina and 4Å mol sieves, the second containing Q5 reactant. The N2, used for transfers, is passed through a single column containing A204 alumna, 4Å mol sieves and Q5. [0145] The reactor is loaded first from the shot tank that contains Isopar E solvent and/or 1-octene, depending on desired reactor loading. The shot tank is filled to the load set points by use of a lab scale to which the shot tank is mounted. After liquid feed addition, the reactor is heated up to the polymerization temperature set point. If ethylene is used, it is added to the reactor when at reaction temperature to maintain reaction pressure set point. Ethylene addition amounts are monitored by a micro-motion flow meter. [0146] The catalyst and co-catalyst components are mixed with the appropriate amount of purified toluene to achieve a solution of the 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 was used, it is then added by the Camile to maintain reaction the pressure set point in the reactor. These polymerizations are run for 10 86026-WO-PCT/DOW 86026 WO minutes, then the agitator is stopped, and the bottom dump valve is opened to empty 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 cooled to ambient temperature, the polymers were weighed for yield/efficiencies, and submitted for polymer testing. [0147] Table 1 presents results of polymerization reactions following the general procedure for the PPR Screening Experiments disclosed herein for various 2-amino-imidazole ligand / heteroleptic cyclopentadienyl metal precursor pairs, comparative 2-amino-imidazole ligand / heteroleptic non-cylcopentadienyl metal precursor pairs, as well as for comparative 2-amino-imidazole ligand / homoleptic metal precursor pairs. TABLE 1: PPR data (averaged over duplicate runs) for various 2-amino-imidazole ligand / heteroleptic and homoleptic metal precursor pairs. 86026-WO-PCT/DOW 86026 WO †Catalyst Activity calculated according to Equation 1: mg of polymer / ((Catalyst Loading (µmol) × Quench Time (sec))/1,800 sec). Higher values indicate higher activity. *Data from WO 2020/263790 A1 using 0.10 µmol MBn4 loadings. [0148] Table 2 presents results of polymerization reactions for Procatalysts 1–3 following the Batch Reactor Polymerization Procedure disclosed herein. The reaction conditions for the results tabulated in Table 2 are as follows: the standard ethylene-octene copolymerization semi-batch reactor conditions of the results in Table 2 for polymerization reaction at 120 °C include 46 g of ethylene, 302 g of 1-octene, 612 g of Isopar E, 1.2 eq. of RIBS-2 activator with respect to catalyst, 10 µmol of MMAO-3A, 290 psi reactor pressure; the standard ethylene-octene copolymerization semi-batch reactor conditions of the results in Table 2 for polymerization reaction at 150 °C include 43 g of ethylene, 301 g of 1-octene, 548 g of Isopar E, 1.2 eq. of RIBS-2 activator with respect to catalyst, 10 µmol of MMAO-3A, 327 psi reactor pressure. TABLE 2: Semi-batch reactor results for ethylene-octene copolymerization for a series of heteroleptic 2-amino-imidazole cyclopentadienyl complexes (Procatalysts 1–3). [0149] As shown by the PPR data presented in Table 1 (IE1–IE4) and the batch reactor data presented in Table 2 below (IE5–IE10), the combination of both a cyclopentadienyl ligand and a 2-amino-imidazole ligand on the same metal center is advantageous for the catalyst activity and polymerization capabilities of the procatalysts described herein. Such control of the activity and polymerization capability provides the ability to tune the performance of catalyst systems and/or achieve different desired polymer properties. 86026-WO-PCT/DOW 86026 WO [0150] For example, as shown by the PPR data presented in Table 1, the heteroleptic 2-amino-imidazole cyclopentadienyl complexes described herein demonstrate the ability for improved catalyst activity relative to their homoleptic analogs and relative to heteroleptic 2-amino-imidazole non-cyclopentadienyl complexes. It should further be noted that significantly higher loadings of the homoleptic precursors were used to achieve catalyst activity further indicating the higher activity of the inventive heteroleptic complexes. [0151] IE1 (cyclopentadienyl precursor nBuCpZrBn3 combined with L-1) has higher PPR catalyst activity than comparatives CE2 and CE3 and comparable activity to CE1, where each of CE1–CE3 have the same L-1 ligand but lack a cyclopentadienyl ligand. It should further be noted that significantly higher loadings of the homoleptic precursors were used to achieve catalyst activity further indicating the higher activity of the inventive heteroleptic complexes. [0152] IE2 (cyclopentadienyl precursor nBuCpZrBn3 combined with L-2) has higher PPR catalyst activity than comparatives CE4–CE6 which have the same L-2 ligand but lack a cyclopentadienyl ligand. [0153] IE3 (cyclopentadienyl precursor nBuCpZrBn3 combined with L-3) has higher PPR catalyst activity than comparatives CE7–CE9 which have the same L-3 ligand but lack a cyclopentadienyl ligand. [0154] IE4 (cyclopentadienyl precursor nBuCpZrBn3 combined with L-4) has higher PPR catalyst activity than comparatives CE10–CE12 which have the same L-4 ligand but lack a cyclopentadienyl ligand. [0155] Furthermore, the data presented in Table 2 of the semi-batch reactor experiments (IE5–IE10) show how the heteroleptic 2-amino-imidazole cyclopentadienyl complexes described herein achieve high catalyst activity and efficiency even at elevated reactor temperatures. In particular, IE5, IE7, and IE9 show how Procatalysts 1–3 all have 120 °C activity ≥ 160,000 g poly/g metal. IE6, IE8, and IE10 show how Procatalysts 1–3 all have 150 °C activity ≥ 180,000 g poly/g metal. Additionally, the data presented in Table 2 of the semi-batch reactor experiments (IE5–IE10) show how the heteroleptic 2-amino-imidazole cyclopentadienyl complexes described herein also achieve high ethylene selectivity, as evidenced by the low 1-octene incorporation levels. IE5–10 show how Procatalysts 1–3 all have ultra-low 1-octene incorporation levels of less than or equal to 0.1 mol% and high Tm at both 120 °C and 150 °C reactor temperatures. This level of ethylene selectivity is beneficial in some applications, often in multi-catalyst or multi-reactor 86026-WO-PCT/DOW 86026 WO configurations where catalyst selectivity is an advantage for achieving precise polymer composition control. [0156] The data presented in Table 2 of the semi-batch reactor experiments (IE5–IE10) also show how the heteroleptic 2-amino-imidazole cyclopentadienyl complexes described herein can achieve a wide range of weight-average molecular weights (Mw) and polydispersity indexes for the resulting polymer through substitution on the cyclopentadienyl ligand. In particular, depending on presence and type of substituents of the cyclopentadienyl ligand, the weight-average molecular weights of the resulting polymer ranged from 48,000 to 210,000 g/mol. Further, depending on the presence and type of substituents of the cyclopentadienyl ligand, the polydispersity index of the resulting polymer ranged from 4.7 to 8.9. Accordingly, the semi-batch reactor results show that the heteroleptic 2-amino-imidazole cyclopentadienyl complexes described herein allow for further control of polymer properties. Measurement Standards Melt and Glass Transition Temperature [0157] Melt temperatures (Tm) and glass transition temperatures (Tg) were measured by differential scanning calorimetry (DSC2500 or Discovery DSC, TA Instruments, Inc.) using a heat-cool-heat temperature profile. Samples of 3-6mg were loaded in open aluminum pans and temperature equilibration was achieved at 200°C. After being held at this temperature for 2 min, the samples were cooled to -90°C at 10°C/min. After being held at -90°C for 4 min, the samples were then heated to 200°C at 10°C/min. Traces of the second heat cycle were analyzed individually using TA Trios software. HT-GPC Analysis with IR Detection of Octene Incorporation [0158] 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. [0159] Decane (10 µL) 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 86026-WO-PCT/DOW 86026 WO concentration of 2 mg/mL. Samples (250 µL) are eluted through one PL-gel 20 µm (50 x 7.5 mm) guard column followed by two PL-gel 20 µm (300 x 7.5 mm) Mixed-A columns maintained at 160 °C with TCB stabilized with BHT at a flowrate of 1.0 mL/min. The total run time is 24 minutes. To calibrate for molecular weight Agilent EasiCal polystyrene standards (PS-1 and PS-2) are diluted with 1.5 mL of TCB stabilized with BHT and dissolved by stirring at 160 °C for 15 minutes. The PS standards are injected into the system without further dilution to create a third- order Mw calibration curve with apparent units adjusted to homo-polyethylene (PE) using known Mark-Houwink coefficients for PS and PE. Octene incorporation is determined using a linear calibration developed by analyzing copolymers of known compositions.

Claims

86026-WO-PCT/DOW 86026 WO CLAIMS 1. A catalyst system comprising a procatalyst having a structure according to Formula (I): where: M is a metal selected from titanium, zirconium, and hafnium, the metal having a formal oxidation state of +2, +3, or +4; each X is a monodentate or bidentate ligand independently selected from unsaturated (C2−C30)hydrocarbon, unsaturated (C2−C30)heterohydrocarbon, (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, halogen, ^N(RX)2, and −(CH2)wSi(RX)3, where w is 1 to 10 and each RX is independently selected from (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, and (C3–C30)heteroaryl; n is 1 or 2; each of R8–12 is independently selected from (C1–C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, −Si(RC)3, −Ge(RC)3, and −H, wherein optionally, any of R8-12 are covalently connected to form one or more aromatic or non-aromatic ring or multi-ring structures; RY is (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, or (C3–C30)heteroaryl; R1 is (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C6–C30)aryl, or (C3–C30)heteroaryl; each of R2 and R3 is independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, 86026-WO-PCT/DOW 86026 WO (C3–C30)heteroaryl, −ORC, −Si(RC)3, −Ge(RC)3, halogen, and –H, wherein R2 and R3 are optionally covalently linked to form an aromatic or non-aromatic ring; 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. 2. The catalyst system of claim 1, wherein: each X is independently selected from (C1−C10)alkyl, (C6−C20)aryl, and halogen; and R1 is (C1−C30)alkyl or (C6−C30)aryl. 3. The catalyst system of any one of the preceding claims, wherein R2 and R3 are covalently linked to form an aromatic ring, and the procatalyst has a structure according to Formula (II): where each R1, RY, R8–12, Q, X, M, and n are defined as in Formula (I); and each of R4, R5, R6, and R7 is independently (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, (C6–C40)aryl, (C3–C40)heteroaryl, halogen, or −H. 4. The catalyst system of claim 3, wherein R4 is (C6−C40)aryl or (C3−C40)heteroaryl. 5. The catalyst system of claim 3, wherein R4 is phenyl, 2,4,6-tri(iso-propyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 3,5-di(tert-butyl)phenyl, unsubstituted naphthyl, substituted naphthyl, unsubstituted carbozolyl, or substituted carbozolyl. 6. The catalyst system of any one of claims 3–5, wherein each of R5 , R6, and R7 is −H. 7. The catalyst system of any one of the preceding claims, wherein R1 is (C6−C30)aryl. 86026-WO-PCT/DOW 86026 WO 8. The catalyst system of any one of the preceding claims, wherein R1 is unsubstituted phenyl, substituted phenyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted naphthyl, or substituted naphthyl. 9. The catalyst system of any preceding claim, wherein R1 is substituted phenyl or unsubstituted phenyl. 10. The catalyst system of any preceding claim, wherein R1 is selected from the group consisting of 2-methylphenyl, 2-(iso-propyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 2,6-di(iso-propyl)phenyl, 2,4,6-tri(iso-propyl)phenyl, 3,5-di(tert-butyl)phenyl, 3,5- diphenylphenyl, 2,3,5,6-tetra-fluorophenyl, or 2-(1-naphthyl)phenyl. 11. The catalyst system of any one of claims 1–6, wherein R1 is (C1−C12)alkyl, (C1−C12)cycloalkyl, trimethylsilyl methyl, benzyl, or 1-adamantyl. 12. The catalyst system of any one of the preceding claims, wherein each of R8-11 is −H and R12 is (C1−C10)alkyl, (C6^C20)aryl, (C1−C20)heterohydrocarbyl, ^Si(RC)3, or ^Ge(RC)3. 13. The catalyst system of any one of claims 1–12, wherein each of R8-R11 is –H and R12 is (C1−C10)alkyl or (C6^C20)aryl. 14. The catalyst system of any one of the preceding claims, wherein each X is independently selected from methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro.
86026-WO-PCT/DOW 86026 WO 15. The catalyst system of any one of the preceding claims, wherein the procatalyst is selected from the group consisting of Procatalyst 1, Procatalyst 2, and Procatalyst 3: Procatalyst 3 16. The catalyst system of any one of the preceding claims, wherein the catalyst system is a supported catalyst system comprising the procatalyst, a support, and an activator. 17. The catalyst system of any one of the preceding claims, wherein the catalyst system comprises a co-catalyst component. 86026-WO-PCT/DOW 86026 WO 18. The catalyst system of claim 17, wherein the co-catalyst component comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof. 19. The catalyst system of any one of claims 17 or 18, wherein the co-catalyst comprises an unsubstituted ammonium borate, a mono-substituted ammonium borate, a bis-substituted ammonium borate, a tri-substituted ammonium borate, or a tetra-substituted ammonium borate. 20. The catalyst system of any one of claims 17 through 19, wherein the co-catalyst component comprises bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine (RIBS-2). 21. A method of making an ethylene-based polymer, the method comprising: polymerizing, via solution phase polymerization in a reactor, 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. 22. The method of claim 21, further comprising feeding hydrogen into the reactor during solution phase polymerization. 23. The method of any one of claims 21 or 22, wherein the method comprises polymerizing the combination of the ethylene monomer and the at least one 1-alkene comonomer, in the presence of the catalyst system of any one of claims 1–20. 24. The method of any one of claims 21 through 23, wherein the ethylene-based polymer comprises at least 95 mol% units derived from ethylene monomer. 25. The method of any one of claims 21 through 24, wherein the ethylene-based polymer comprises at least 99.5 mol% units derived from ethylene monomer. 26. The method of any one of claims 21 through 25, wherein the ethylene-based polymer comprises a weight-average molecular weight of less than or equal to 250,000 g/mol. 86026-WO-PCT/DOW 86026 WO 27. The method of any one of claims 21 through 26, wherein the at least one 1-alkene comonomer comprises 1-butene, 1-hexene, or 1-octene.
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