Heteroleptic cyclopentadienyl complexes bearing 2-amino-thiazole ligands

Abstract

Catalyst systems comprising a procatalyst having a structure according to Formula (I): [insert formula] where M is a metal chosen from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +3 or +4; each X is a monodentate or bidentate ligand; n is 1 or 2; each of R8−R12 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−R12 are covalently connected to form one or more ring or multi-ring structures; R1 is a (C­1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C6-C30)aryl, or (C3-C30)heteroaryl; each 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 ring or a 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.

Description

86019-WO-PCT / DOW 86019 WO -1- HETEROLEPTIC CYCLOPENTADIENYL COMPLEXES BEARING 2-AMINO- THIAZOLE LIGANDS CROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 665,661 filed June 28, 2024, the entire disclosure of which is hereby incorporated by reference. TECHNICAL FIELD

[0002] Embodiments of the present disclosure generally relate to catalyst systems and processes that may be utilized for olefin polymerization, and, more specifically, to catalyst systems involving Group IV heteroleptic cyclopentadiene complexes bearing 2-amino-thiazole ligands and to olefin polymerization processes incorporating such catalyst systems. BACKGROUND

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

[0004] Ethylene-based polymers are manufactured for a wide variety of articles. The polyethylene polymerization process can be varied in a number of respects to produce a wide variety of resultant polyethylene resins having different physical properties that render the various resins suitable for use in different applications. The ethylene monomers and, optionally, one or more co-monomers are present in liquid diluents (such as solvents), such as an alkane or isoalkane, such as isoparaffin liquids (i.e. Isopar-E). Hydrogen may also be added to the reactor. The catalyst systems for producing ethylene-based may typically comprise a chromium-based catalyst system, a Ziegler–Natta catalyst system, and / or a molecular (either metallocene or non-metallocene (molecular)) catalyst system. The reactants in the diluent and the catalyst system are circulated at an elevated polymerization temperature around the reactor, thereby producing ethylene-based homopolymer or copolymer. Either periodically or continuously, part of the reaction mixture, including the polyethylene product dissolved in the diluent, together with unreacted ethylene and one or more optional co-monomers, is removed from the reactor. The reaction mixture, when86019-WO-PCT / DOW 86019 WO -2- removed from the reactor, may be processed to remove the polyethylene product from the diluent and the unreacted reactants, with the diluent and unreacted reactants typically being recycled back into the reactor. 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. Despite the research efforts in developing catalyst systems suitable for olefin polymerization, such as polyethylene polymerization, there is still a need to increase the efficiencies of catalyst systems that are capable of producing polymer with high ethylene selectivity and a range of molecular weight capabilities. SUMMARY

[0005] Embodiments of this disclosure include catalysts systems. According to a first aspect of the present disclosure, the catalyst system includes a procatalyst having a structure according to Formula (I):

[0006] In Formula (I), M is a metal chosen from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +3 or +4. Each X is a monodentate or bidentate ligand independently chosen 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 RXis independently selected from a (C1−C30)hydrocarbyl and (C1−C30)heterohydrocarbyl. Formula (I) is overall charge neutral; n is 1 or 2.

[0007] In Formula (I), each R8–R12is 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 R8-12are covalently connected to form one or more ring or multi-ring structures; R1is a (C1–C30)hydrocarbyl, or (C1–C30)heterohydrocarbyl; each R2and R3is independently selected from the group consisting of (C1−C30)hydrocarbyl,86019-WO-PCT / DOW 86019 WO -3- (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, −ORC, −Si(RC)3, −Ge(RC)3, halogen, and –H, wherein R2and R3are optionally covalently linked to form an aromatic ring or a non-aromatic ring; and each RCis independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, and –H.

[0008] A second aspect includes the first aspect, wherein: each X is independently selected from (C1−C10)alkyl, (C6^C20)aryl, and halogen; and R1is a (C1−C30)alkyl or a (C6−C30)aryl.

[0009] A third aspect includes either one of the first or second aspects, wherein R2and R3are covalently linked to form an aromatic ring, and the procatalyst has a structure according to Formula (II):where each R1, R8−R12, X, n, and M are defined as in Formula (I); and each R4, R5, R6, and R7is independently (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, (C6-C40)aryl, (C3- C40)heteroaryl, a halogen, or –H.

[0010] A fourth aspect includes the third aspect, wherein R4is (C6−C40)aryl or (C3−C40)heteroaryl.

[0011] A fifth aspect includes athe third aspect, wherein R4is 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.

[0012] A sixth aspect includes any one of the third through fifth aspects, wherein each of R5, R6, and R7are −H.

[0013] A seventh aspect includes any one of the first through sixth aspects, wherein R1is (C6−C30)aryl.

[0014] An eighth aspect includes any one of the first through seventh aspects, wherein R1is unsubstituted phenyl, substituted phenyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted naphthyl, or substituted naphthyl.86019-WO-PCT / DOW 86019 WO -4-

[0015] A ninth aspect includes any one of the first through eighth aspects, wherein R1is substituted phenyl or unsubstituted phenyl.

[0016] A tenth aspect includes any one of the first through ninth aspects, wherein R1is 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..

[0017] An eleventh aspect includes any one of the first through sixth aspects, wherein R1is (C1−C12)alkyl, (C1−C12)cycloalkyl, trimethylsilyl methyl, benzyl, or 1-adamantyl.

[0018] A twelfth aspect includes any one of the first through eleventh aspects, wherein each X is independently selected from methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro.

[0019] A thirteenth aspect includes any one of the first through twelfth aspects, wherein each of R8−R11is –H and R12is (C1−C10)alkyl, (C6^C20)aryl, (C1−C20)heterohydrocarbyl, ^Si(RC)3, or ^Ge(RC)3..

[0020] A fourteenth aspect includes any one of the first through twelfth aspects, wherein each of R8−R11is –H and R12is (C1−C10)alkyl or (C6^C20)aryl.

[0021] A fifteenth aspect includes any one of the first through fourteenth aspects, wherein the procatalyst has a structure according to any one of formulas:Procatalyst 1 Procatalyst 286019-WO-PCT / DOW 86019 WO -5-Procatalyst 5 Procatalyst 6Procatalyst 9 Procatalyst 1086019-WO-PCT / DOW 86019 WO -6-

[0022] A sixteenth aspect includes any one of the first through fifteenth aspects, wherein the catalyst system is a supported catalyst system comprising the procatalyst, a support, and an activator.

[0023] A seventeenth aspect includes any one of the first through sixteenth aspects, wherein the catalyst system comprises a co-catalyst component.

[0024] An eighteenth aspect includes the seventeenth aspect, wherein the co-catalyst component comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.

[0025] A nineteenth aspect includes either one of the seventheeth or eighteenth aspects, wherein the co-catalyst component comprises an unsubstituted ammonium borate, a mono- substituted ammonium borate, a bi-substituted ammonium borate, a tri-substituted ammonium borate, or a tetra-substituted ammonium borate.

[0026] A twentieth aspect includes any one of the seventeenth through nineteenth aspects, wherein the co-catalyst component comprises bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine (RIBS-2).

[0027] A twenty-first aspect is directed to a method of making an ethylene-based polymer comprising polymerizing ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of the catalyst system of any one of the first through twentieth aspects, wherein the polymerizing comprises solution polymerization.

[0028] A twenty-second aspect includes the twenty-first aspect, further comprising feeding hydrogen into the reactor during solution polymerization.

[0029] A twenty-third aspect includes either one of the twenty-first or twenty-second aspects, wherein the method comprises polymerizing the combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of the catalyst system of any one of the first through twentieth aspects.

[0030] A twenty-fourth aspect includes the twenty-third aspect, wherein the ethylene-based polymer comprises greater than or equal to 95 mol% ethylene.

[0031] A twenty-fifth aspect includes any one of the twenty-first through twenty-fourth aspects, wherein a weight average molecular weight of the ethylene-based polymer is less than or equal to 250,000 g / mol.86019-WO-PCT / DOW 86019 WO -7-

[0032] Embodiments of this disclosure include polymerization processes, particularly methods of making ethylene-based polymers. The methods of making include polymerizing ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of the catalyst system including a procatalyst having a structure according to Formula (I), wherein the polymerizing comprises solution polymerization. DETAILED DESCRIPTION

[0033] 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.

[0034] Common abbreviations are listed below:

[0035] R, Q, M, X and n: as defined above; Me : methyl; Et : ethyl; Ph : phenyl; Bn: benzyl; Mes: mesityl (2,4,6-trimethylphenyl); i-Pr : iso-propyl; t-Bu : tert-butyl; t-Oct : tert-octyl (2,4,4- trimethylpentan-2-yl); Tf : trifluoromethane sulfonate; : Et2O : diethyl ether; EtOH : ethanol; DCM or CH2Cl2 : dichloromethane; DME : dimethoxyethane; DIW : deionized water; C6D6 : deuterated benzene or benzene-d6 : CDCl3 : deuterated chloroform; Na2SO4 : sodium sulfate; M: magnesium sulfate; HCl : hydrogen chloride; K2CO3: potassium carbonate; NaHCO3 : sodium bicarbonate; NH4Cl : ammonium chloride; Pd(Ph3)4 : tetrakis(triphenylphosphine)palladium(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; Cp*ZrBn3: pentamethylcyclopentadienylzirconium(IV) tribenzyl;MeCpZrBn3: methylcyclopentadienylzirconium(IV) tribenzyl; N2 : nitrogen gas; PhMe: toluene; PPR : parallel pressure reactor; MAO : methylaluminoxane; MMAO : modified methylaluminoxane; 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; mmol : millimoles; mL : milliliters; M : molar; min or mins: minutes; h or hrs : hours; d: days; rpm: revolution per minute.86019-WO-PCT / DOW 86019 WO -8-

[0036] 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.

[0037] 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.

[0038] The term “independently selected” followed by multiple options is used herein to indicate that the individual R groups appearing before the term, such as R1, R2, R3, R4, R5, and RCcan be identical or different, without dependency on the identity of any other Group also appearing before the term.

[0039] The term “procatalyst” refers to a compound that has catalytic activity when combined with an activator. The term “activator” refers to a compound that chemically reacts with a procatalyst in a manner that converts the procatalyst to a catalytically active catalyst. As used herein, the terms “co-catalyst” and “activator” are interchangeable terms.

[0040] 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 RSsubstituted version of a chemical Group defined using the “(Cx^Cy)” parenthetical may contain more than y carbon atoms depending on the identity of any groups RS. For example, a “(C1^C50)alkyl substituted with exactly one Group RS, where RSis 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 the86019-WO-PCT / DOW 86019 WO -9- chemical Group is determined by adding to both x and y the combined sum of the number of carbon atoms from all of the carbon atom-containing substituents RS.

[0041] 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.

[0042] 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 RSor unsubstituted.

[0043] In this disclosure, a (C1^C50)hydrocarbyl may be an 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)).

[0044] In this disclosure, a (C1^C30)hydrocarbyl may be an 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)).

[0045] 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; unsubstituted86019-WO-PCT / DOW 86019 WO -10- (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 (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.

[0046] The term “(C6^C30)aryl” means an unsubstituted or substituted (by one or more RS) mono-, bi- or tricyclic aromatic hydrocarbon radical of from 6 to 30 carbon atoms, of which at least from 6 to 14 of the carbon atoms are aromatic ring carbon atoms. Other aryl groups (e.g., (Cx^Cy)aryl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more RS. A monocyclic aromatic hydrocarbon radical includes one aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or non-fused and aromatic or non- aromatic. Examples of unsubstituted (C6^C30)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^C30)aryl include: substituted (C1^C20)aryl; substituted (C6^C18)aryl; 2,4-bis([C20]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9- one-l-yl.

[0047] 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.86019-WO-PCT / DOW 86019 WO -11-

[0048] 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 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.

[0049] 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 RSmay 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.

[0050] 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.

[0051] 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),86019-WO-PCT / DOW 86019 WO -12- N(RN), ^N=C(RC)2, −Ge(RC)2−, or ^Si(RC)^, where each RCand each RPis unsubstituted (C1^C18)hydrocarbyl or ^H, and where each RNis unsubstituted (C1−C18)hydrocarbyl. The term “heterohydrocarbon” refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. The term “(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.

[0052] 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.

[0053] The (C1^C30)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (C1^C30)heterohydrocarbyl include (C1^C50)heteroalkyl, (C1^C30)hydrocarbyl-O^, (C1^C30)hydrocarbyl-S^, (C1^C30)hydrocarbyl-S(O)^,86019-WO-PCT / DOW 86019 WO -13- (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- (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.

[0054] 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 tricyclyc 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 the86019-WO-PCT / DOW 86019 WO -14- 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.

[0055] 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.

[0056] 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.

[0057] 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−).

[0058] 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.

[0059] Embodiments of this disclosure include catalysts systems. The catalyst system includes a procatalyst having a structure according to Formula (I):86019-WO-PCT / DOW 86019 WO -15-

[0060] In Formula (I), M is a metal chosen from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +3 or +4. Subscript n of (X)nis 1 or 2. Each X is a monodentate or bidentate ligand independently chosen 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 RXis independently selected from a (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, and (C3-C30)heteroaryl.

[0061] In Formula (I), R1is a (C1−C50)hydrocarbyl (C1−C50)heterohydrocarbyl, (C6-C30)aryl, or (C3-C30)heteroaryl. Each R2and R3is 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 R2and R3are optionally covalently linked to form an aromatic ring or a non-aromatic ring, and each RCis independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, and –H. Each of R8-12is 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 R8-12are covalently connected to form one or more ring or multi-ring structures.

[0062] In one or more embodiments, in Formula (I), each X is independently selected from (C1−C10)alkyl, (C6^C20)aryl, and a halogen and R1 is a (C1−C30)alkyl or a (C6−C30)aryl.

[0063] In one or more embodiments, in Formula (I), R1is (C6−C30)aryl.

[0064] In one or more embodiments, R1is unsubstituted phenyl, substituted phenyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted naphthyl, or substituted naphthyl. In various embodiments, R1is unsubstituted phenyl or substituted phenyl.86019-WO-PCT / DOW 86019 WO -16-

[0065] In various embodiments, R1is 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, and 2-(1-naphthyl)phenyl.

[0066] In one or more embodiments, R1is (C1−C12)alkyl, (C1−C12)cycloalkyl, trimethylsilyl methyl, benzyl, or 1-adamantyl.

[0067] In one or more embodiments, the (C1−C30)hydrocarbyl of R2and R3may be a (C6−C30)aryl and the (C1−C30)heterohydrocarbyl of R2and R3may be a (C3−C30)heteroaryl.

[0068] In one or more embodiments, the (C1−C30)heterohydrocarbyl of R2and R3may be covalently linked to form an aromatic ring or a non-aromatic ring.

[0069] In one or more embodiments, each X is independently selected from methyl, benzyl, phenyl, trimethylsilyl methyl, or chloro.

[0070] In one or more embodiments, in Formula (I), each of R8-R12is independently selected from (C1−C10)alkyl, (C6^C20)aryl, (C1−C20)heterohydrocarbyl, ^Si(RC)3, ^Ge(RC)3, and –H. In one or more embodiments, in Formula (I), each of R7-R11is –H and R12is (C1−C10)alkyl, (C6^C20)aryl, (C1−C20)heterohydrocarbyl, ^Si(RC)3, or ^Ge(RC)3.

[0071] In various embodiments wherein R2and R3are covalently linked to form an aromatic ring, the procatalyst may have a structure according to Formula (II):

[0072] In Formula (II), each R1, R8-12, X, n, and M are defined as in Formula (I); and each R4, R5, R6, and R7are independently (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, a halogen, or –H.86019-WO-PCT / DOW 86019 WO -17-

[0073] In various embodiments, R4is (C6−C30)aryl or (C3−C30)heteroaryl.

[0074] In one or more embodiments, R4is 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.

[0075] In various embodiments, R5, R6, and R7, are –H.

[0076] In various embodiments, R1is (C6−C30)aryl; R4is 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 R5,R6, and R7,are −H.

[0077] In some embodiments of this disclosure, in Formulas (I) and (II), n is 2. In other embodiments, n is 1. In other embodiments, n is 1 or 2.

[0078] 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 has 6 or fewer metal^ligand bonds and can be overall charge-neutral or may have a positive-charge associated with the metal center.

[0079] 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. Monoanionic ligands have a net formal oxidation state of −1. 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 RMindependently is hydrogen, (C1^C20)hydrocarbyl, or (C1^C20)heterohydrocarbyl, or RKand RLare taken together to form a (C2^C20)hydrocarbylene or (C1^C20)heterohydrocarbylene and RMis as defined above.

[0080] 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 RQNRKRL, RKORL, RKSRL, or RQPRKRL, where each RQindependently is86019-WO-PCT / DOW 86019 WO -18- hydrogen, [(C1^C10)hydrocarbyl]3Si(C1^C10)hydrocarbyl, (C1^C20)hydrocarbyl, [(C1^C10)hydrocarbyl]3Si, or (C1^C20)heterohydrocarbyl and each RKand RLindependently is as previously defined.

[0081] 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 RKand RLindependently 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 RKand RLindependently is an unsubstituted (C1^C10)hydrocarbyl. In one or more embodiments of Formula (I) and (II), X is benzyl, chloro, −CH2SiMe3, or phenyl.

[0082] In further embodiments, each X is independently selected from (C1−C10)alkyl, (C6^C20)aryl, and a halogen.

[0083] 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.

[0084] In further embodiments, each X is independently selected from methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro.

[0085] In some embodiments, any or all of the chemical groups (e.g., X, R1−R3, and R8−R12) of the procatlayst of Formula (I) may be unsubstituted. In other embodiments, none, any, or all of the chemical groups X, R1−R3, and R8−R12of the procatalyst of Formula (I) may be substituted with one or more than one RS. When two or more than two RSare bonded to a same chemical group of the metal^ligand complex of Formula (I), the individual RSof the chemical group may be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, none, any, or all of the chemical groups X, R1−R3, and R8−R12may be86019-WO-PCT / DOW 86019 WO -19- persubstituted with RS. In the chemical groups that are persubstituted with RS, the individual RSmay all be the same or may be independently chosen.

[0086] 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, or all of the chemical groups X, R1, R4−R7,and R8−R12of the procatalyst of Formula (II) may be substituted with one or more than one RS. When two or more than two RSare bonded to a same chemical group of procatalyst of Formula (II), the individual RSof the chemical group may be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, none, any, or all of the chemical groups X, R1, R4−R7,and R8−R12may be persubstituted with RS. In the chemical groups that are persubstituted with RS, the individual RSmay all be the same or may be independently chosen.

[0087] In illustrative embodiments, the catalyst systems may include a procatalyst according to Formula (I) having the structure of any of the Procatalysts 1 – 10 listed below:Procatalyst 3 Procatalyst 486019-WO-PCT / DOW 86019 WO -20-

[0088] Embodiments of this disclosure includes polymerization processes. The polymerization processes include polymerizing ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer in the presence of a catalyst system comprising a procatalyst according to Formula (I).86019-WO-PCT / DOW 86019 WO -21- Co-catalyst Component

[0089] 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 complex to, or combining the complex with, an activating co-catalyst. 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 a benzyl or phenyl. Suitable activating co-catalysts for use herein include alkyl aluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). 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.

[0090] 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 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.86019-WO-PCT / DOW 86019 WO -22-

[0091] 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.

[0092] The catalyst system that includes the procatalyst of Formula (I) may be activated to form an active catalyst composition by combination with one or more co-catalysts, for example, a cation forming co-catalyst, a strong Lewis acid, or combinations thereof. Suitable activating co- catalysts include polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as inert, compatible, noncoordinating, ion forming compounds. Exemplary suitable co-catalysts include, but are not limited to modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1−) amine (RIBS-2), and combinations thereof.

[0093] In particular embodiments, the co-catalyst comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), triethylaluminum (TEA), or combinations thereof.

[0094] In particular embodiments, the 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.

[0095] In particular embodiments, the co-catalyst comprises bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine (RIBS-2).

[0096] In some embodiments, more than one of the foregoing activating co-catalysts may be used in combination with each other. A specific Example of a 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 1:5000, in some other embodiments, at least 1: 1000; and 10:1 or less, and in some other embodiments, 1:1 or less.86019-WO-PCT / DOW 86019 WO -23- 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 metal–ligand complexes of Formula (I) from 0.5: 1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activating co-catalysts are generally employed in approximately mole quantities equal to the total mole quantities of one or more procatalysts of Formula (I).

[0097] In some embodiments, when more than one of the foregoing co-catalysts is used in combination, one or more of the co-catalysts may function as a scavenger. The purpose of the scavenger may be 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.

[0098] In some embodiments, the co-catalyst 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.

[0099] In some embodiments, the co-catalyst 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. Supported Catalyst Systems

[0100] 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-catalyst86019-WO-PCT / DOW 86019 WO -24- 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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., as86019-WO-PCT / DOW 86019 WO -25- 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.

[0106] 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.

[0107] 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.

[0108] 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 some86019-WO-PCT / DOW 86019 WO -26- 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.

[0109] 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. Polyolefins

[0110] 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 co- monomers typically have no more than 20 carbon atoms. For example, the α-olefin co-monomers may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin co-monomers 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 co-monomers 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.

[0111] The ethylene-based polymers, for example homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more co-monomers such as α-olefins,86019-WO-PCT / DOW 86019 WO -27- may comprise from at least 50 percent by weight monomer units derived from ethylene. 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 co-monomers 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.

[0112] In some embodiments, the ethylene-based polymers may comprise at least 90 mole percent units derived from ethylene. All individual values and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymers may comprise at least 93 mole percent units derived from ethylene; at least 95 mole percent units; at least 96 mole percent units; at least 97 mole percent units derived from ethylene; or in the alternative, from 90 to 100 mole percent units derived from ethylene; from 90 to 99.5 mole percent units derived from ethylene; or from 97 to 99.5 mole percent units derived from ethylene.

[0113] In some embodiments of the ethylene-based polymer, the amount of additional ^-olefin is less than 50%; other embodiments include at least 0.5 mole percent (mol%) to 25 mol%; and in further embodiments the amount of additional ^-olefin includes at least 5 mol% to 10 mol%. In some embodiments, the additional ^-olefin is 1-octene.

[0114] In embodiments, a weight average molecular weight of the ethylene-based polymer may be less than or equal to 250,000 g / mol. For example, the weight average molecular weight of the ethylene-based polymer may be less than or equal to 225,000 g / mol, less than or equal to 200,000 g / mol, less than or equal to 175,000 g / mol, less than or equal to 150,000 g / mol, less than or equal to 100,000 g / mol, less than or equal to 75,000 g / mol, less than or equal to 50,000 g / mol, less than or equal to 40,000 g / mol, less than or equal to 30,000 g / mol, or less than or equal to 20,000 g / mol. Polymerization Processes

[0115] As noted above, embodiments of this disclosure include polymerization processes. The polymerization processes include polymerizing, via solution phase polymerization in a reactor,86019-WO-PCT / DOW 86019 WO -28- 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.

[0116] 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, and as described herein, and optionally one or more other catalysts. 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.

[0117] In another embodiment, the ethylene-based polymer may be produced via solution polymerization in a single reactor system, for example a 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 cocatalysts, as described in the preceding paragraphs.

[0118] In embodiments, the methods of producing the ethylene-based polymer may comprise feeding hydrogen into the reactor during solution polymerization.86019-WO-PCT / DOW 86019 WO -29-

[0119] 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.

[0120] 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). The polymer resulting from such a catalyst system that incorporates the procatalyst of Formula (I) may have a density according to ASTM D792 (incorporated herein by reference in its entirety) from 0.850 g / cm3to 0.970 g / cm3, from 0.870 g / cm3to 0.950 g / cm3, from 0.880 g / cm3to 0.920 g / cm3, from 0.880 g / cm3to 0.910 g / cm3, from 0.900 g / cm3to 0.950 g / cm3, from 0.920 g / cm3to 0.950 g / cm3, from 0.950 g / cm3to 0.970 g / cm3, or from 0.880 g / cm3to 0.900 g / cm3, for example.

[0121] In another embodiment, the polymer resulting from the catalyst system that includes the metal–ligand complex 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.

[0122] In some embodiments, the polymer resulting from the catalyst system that includes the metal–ligand complex of Formula (I) has a molecular-weight distribution (MWD) from 1 to 25, where MWD is defined as Mw / Mnwith Mwbeing a weight-average molecular weight and Mnbeing a number-average molecular weight. In other embodiments, the polymers resulting from the catalyst system have a MWD from 1 to 8. Another embodiment includes a MWD from 1 to 5;86019-WO-PCT / DOW 86019 WO -30- other embodiments include a MWD from 1 to 4; and other embodiments include MWD from 1.5 to 2.5.

[0123] Embodiments of the catalyst systems described in this disclosure yield unique polymer properties as a result of the high molecular weights of the polymers formed and the amount of the co-monomers incorporated into the polymers.

[0124] 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 andnBuCpZrCl3 were purchased from either Strem Chemicals or Sigma Aldrich. 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 ionizing agent. HRMS analyses were performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8μm 2.1x50 mm coupled with an Agilent 6230 TOF MassSpectrometer with electrospray data are reported as follows: chemical shift (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = = 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 with1H 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. General Procedure for PPR Screening Experiments

[0125] 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 for86019-WO-PCT / DOW 86019 WO -31- 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, chain shuttling agent solutions as appropriate to the experiment, and catalyst solutions) are added to the single-cell reactors via robotic syringes. Gaseous reagents (i.e., ethylene, H2) 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.

[0126] A portion of Isopar-E is added to the reactors. The reactors are heated to the run temperature and pressured to the appropriate psig with ethylene. Toluene solutions of reagents are added in the following order: (1) 1-octene with 500 nmol of scavenger MMAO-3A; (2) 1.5 equiv activator (RIBS-II); and (3) catalyst (20 nmol).

[0127] Each liquid addition was chased with a small amount of Isopar E so that after the final addition a total reaction volume of 5 mL was reached. Upon addition of the catalyst, the PPR software began monitoring the pressure of each cell. The desired pressure (within approximately 2–6 psig) was maintained by the supplemental addition of ethylene gas by opening the valve at the set point minus 1 psi and closing it when the pressure reached 2 psi higher. All drops in pressure were cumulatively recorded as “Uptake” or “Conversion” of the ethylene for the duration of the run or until the uptake or conversion requested value was reached, whichever occurred first. Each reaction was 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. In order to prevent the formation of too much polymer in any given cell, the reaction was quenched upon reaching a predetermined uptake level (50 psig). After the reaction mixtures were quenched, cooled to 70 °C, vented, purged for 5 minutes with nitrogen to remove carbon monoxide, and the tubes were removed. The polymer samples were 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. HT-GPC Analysis with IR Detection of Octene Incorporation

[0128] High-temperature GPC analysis was performed using a Dow Robot Assisted Delivery (RAD) system equipped with a PolymerChar infrared detector (IR5) and Agilent PLgel Mixed A columns. Decane (10 µL) was added to each sample for use as an internal flow marker. Samples were first diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300 ppm of butylated86019-WO-PCT / DOW 86019 WO -32- hydroxytoluene (BHT) to a concentration of 10 mg / mL and dissolved by stirring at 160 °C for 120 minutes. Prior to injection samples were further diluted with TCB stabilized with BHT to a concentration of 2 mg / mL. Samples (250 µL) were 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 was 24 minutes. To calibrate for molecular weight Agilent EasiCal polystyrene standards (PS-1 and PS- 2) were diluted with 1.5 mL of TCB stabilized with BHT and dissolved by stirring at 160 °C for 15 minutes. The PS standards were injected into the system without further dilution to create a third-order Mwcalibration curve with apparent units adjusted to homo-polyethylene (PE) using known Mark-Houwink coefficients for PS and PE. Octene incorporation was determined by use of a linear calibration developed by analyzing copolymers of known compositions. Melt and Glass Transition Temperature

[0129] 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. Batch Reactor Polymerization Procedure

[0130] The batch reactor polymerizations were conducted in a 2-L Parr™ batch reactor. The reactor is heated by an electrical heating mantle and is cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating / cooling system are controlled and monitored by a Camile™ TG process computer. The bottom of the reactor is fitted with a dump valve, which empties the reactor contents into a stainless-steel dump pot, which is prefilled with a catalyst kill solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). The dump pot is vented to a 30-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 were passed through two columns, the first containing activated A2 alumina, the second containing activated Q5 reactant. The ethylene was passed through two columns, the first containing A204 alumina86019-WO-PCT / DOW 86019 WO -33- and 4Å mol sieves, the second containing Q5 reactant. The N2, used for transfers, was passed through a single column containing A204 alumna, 4Å mol sieves and Q5.

[0131] 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.

[0132] The catalyst and co-catalysts were mixed with the appropriate amount of purified toluene to achieve a solution of the desired molarity. The catalyst and co-catalyst components were handled in an inert glove box, drawn into a syringe and pressure transferred into the catalyst shot tank. This was followed by three rinses of toluene, 5 mL each. Immediately after catalyst addition the run timer began. If ethylene was used, it was then added by the Camile to maintain reaction the pressure set point in the reactor. These polymerizations were run for 10 min., then the agitator was stopped, and the bottom dump valve was opened to empty reactor contents into the dump pot. The dump pot contents were poured into trays placed in a lab hood where the solvent was evaporated off overnight. The trays containing the remaining polymer were then transferred to a vacuum oven, where they were heated up to 140 °C under vacuum to remove any remaining solvent. After the trays cooled to ambient temperature, the polymers were weighed for yield / efficiencies, and submitted for polymer testing. EXAMPLES

[0133] Examples 1 to 20 are synthetic procedures for ligand intermediates, ligands, and isolated procatalysts. Procatalysts 1 to 10 were synthesized from the Ligands 1 to 4. In Example 21, the results of the polymerization reactions of Procatalysts 1 – 10 are tabulated and discussed. One or more features of the present disclosure are illustrated in view of the examples as follows:86019-WO-PCT / DOW 86019 WO -34- Example 1 3-bromo-2',4',6'-trimethyl-[1,1'-biphenyl]-2-amine

[0134] Under N2atmosphere, 2,6-dibromoaniline (10.0 g, 39.9 mmol, 1.0 equiv), a magnetic stir bar, toluene (250 mL), and 1 M aqueous solution of K2CO3 in water (120 mL, 3 equiv of base) to a 3-neck 1L round bottom flask at ambient temperature. The biphasic mixture was de- oxygenated by bubbling N2through the mixture for 60 min at ambient temperature. In a separate 100 mL round bottom flask, the mesitylboronic acid (6.84 g, 41.7 mmol, 1.04 equiv) was combined with EtOH (80 mL) and allowed to stir until fully dissolved. The solution of boronic acid in EtOH was then added to the biphasic mixture of aniline, toluene and water, and the combined mixture was then sparged for an additional 30 min with N2 while vigorously stirring. After this time, the Pd(PPh3)4 catalyst (2.31 g, 2.00 mmol, 0.05 equiv) was added to the mixture in one lot at ambient temperature. A water-cooled reflux condenser was installed, and the reaction mixture was heated under N2 at 95 °C for 72 h. After cooling, the biphasic solution was diluted with 600 mL of NH4Cl and 600 mL of DCM and transferred to a separatory funnel and shaken. The organic phase was separated and washed alternately with water (2 x 300 mL) and saturated NaHCO3(aq) (2 x 300 mL). The organic phase was then dried over Na2SO4, filtered, and concentrated using a rotovap to afford an oil. The crude product was subjected to ISCO column chromatography on silica gel with a 0 to 40 % gradient ethyl acetate in hexanes as the solvent system. The impure material was further purified by reverse phase ISCO column chromatography with a 30 to 100 % gradient acetonitrile in water solvent system. The purified material was collected as a pale-yellow oil. Yield: 5.22 g, 45.1 %.

[0135] 1H NMR (400 MHz, CDCl3) δ 7.41 (ddd, J = 8.0, 1.5, 0.6 Hz, 1H), 6.97 (s, 2H), 6.86 (ddd, J = 7.4, 1.5, 0.5 Hz, 1H), 6.67 (ddd, J = 7.9, 7.3, 0.6 Hz, 1H), 3.84 (s, 2H), 2.33 (s, 3H), 2.00 (s, 6H).13C NMR (101 MHz, CDCl3) δ 141.7, 137.62, 137.1, 134.5, 131.5, 129.3, 128.7, 127.3, 119.0, 109.4, 21.2, 20.2.86019-WO-PCT / DOW 86019 WO -35- Example 2 3-bromo-2-isothiocyanato-2',4',6'-trimethyl-1,1'-biphenyl

[0136] To a solution of 2-bromo-6-mesitylaniline (5.2 g, 17.9 mmol, 1 equiv) in DCM (25 mL) was added a solution of sat. aq. NaHCO3 (25 mL). The reaction mixture was cooled to 0 °C, and thiophosgene (3.58 mL, 46.6 mmol, 2.6 equiv) was added dropwise over the course of 15 min. The resulting red-orange reaction mixture was allowed to warm to ambient temperature and continue stirring vigorously for 48 hr. The mixture was then diluted with DCM (125 mL) and washed with brine (2 x 65 mL). The layers were separated, and the organic layer was dried over MgSO4, filtered, and concentrated in vacuo to afford an orange oil. The crude product was purified by ISCO column chromatography on silica gel with a 0 to 20 % gradient ethyl acetate in hexanes as the solvent system. The purified material was collected as pale-yellow crystals. Yield: 4.41 g, 74.1%.

[0137] 1H NMR (400 MHz, CDCl3) δ 7.58 (dd, J = 8.0, 1.5 Hz, 1H), 7.18 (t, J = 7.8 Hz, 1H), 7.12 (dd, J = 7.6, 1.6 Hz, 1H), 6.96 (s, 2H), 2.35 (s, 3H), 1.98 (s, 6H).13C NMR (101 MHz, CDCl3) δ 141.0, 138.3, 136.28, 134.3, 132.0, 129.8, 128.4 (2C), 128.0, 119.9, 21.3, 20.3. *Isothiocyanate carbon resonance is not present. Example 3 Ligand 1. N-phenyl-4-mesityl-benzothiazole-amine

[0138] In a nitrogen filled glovebox, 2-bromo-6-mesityl-isothiocyanate (1.00 g, 3.02 mmol, 1 equiv), DME (10 mL), and a magnetic stir bar were added to a 20 mL glass vial. The contents were stirred at ambient temperature for 2 min, affording a colorless solution. Separately, DME86019-WO-PCT / DOW 86019 WO -36- (8 mL) and aniline (0.55 mL, 6.03 mmol, 2 equiv) were combined in an 8 mL vial. The solution of aniline was added dropwise to the stirring solution of isothiocyanate at ambient temperature. The resulting solution was then allowed to continue stirring at ambient temperature overnight for 18 h to allow the thiourea intermediate to form. The next day, copper (I) iodide (57 mg, 0.30 mmol, 0.1 equiv) and 1,10-phenanthroline (54 mg, 0.30 mmol, 0.1 equiv) were added directly as solids to the reaction mixture, followed quickly by the addition of cesium carbonate (1.97 g, 6.03 mmol, 2 equiv). The resulting heterogeneous mixture was heated to 75 °C and allowed to continue stirring at this temperature for 4 h. The mixture was then allowed to cool to ambient temperature, removed from the glovebox, diluted with ethyl acetate (250 mL), washed with water (2 x 250 mL), and then washed with brine (2 x 250 mL). The organic layer was dried over MgSO4, filtered, and concentrated to afford a pale brown residue. The material was further purified by ISCO column chromatography using 0 to 20 % gradient ethyl acetate in hexanes as the solvent system. The purified material was collected as a colorless solid. Yield: 0.86 g, 82.9 %.1H NMR (500 MHz, CDCl3) δ 7.63 (dd, J = 7.9, 1.3 Hz, 1H), 7.40 (s, 1H), 7.35 (dd, J = 8.6, 7.2 Hz, 2H), 7.32 – 7.29 (m, 2H), 7.21 (t, J = 7.6 Hz, 1H), 7.15 – 7.09 (m, 2H), 6.98 (s, 2H), 2.35 (s, 3H), 2.02 (s, 6H).13C NMR (101 MHz, CDCl3) δ 163.0, 150.0, 140.1, 136.9, 136.5, 136.4, 132.2, 130.5, 129.5, 128.2, 127.6, 123.9, 122.5, 119.7, 119.5, 21.3, 20.8. Example 4 Ligand 2. N-(2,6-dimethylphenyl)-4-mesitylbenzothiazole-amine

[0139] In a nitrogen filled glovebox, 2-bromo-6-mesityl-isothiocyanate (1.00 g, 3.02 mmol, 1 equiv), DME (10 mL), and a magnetic stir bar were added to a 20 mL glass vial. The contents were stirred at ambient temperature for 2 min, affording a colorless solution. Separately, DME (8 mL) and 2,6-dimethylphenylaniline (0.74 mL, 6.03 mmol, 2 equiv) were combined in an 8 mL vial. The solution of 2,6-dimethylphenylaniline was added dropwise to the stirring solution of isothiocyanate at ambient temperature. The resulting mixture was then allowed to continue stirring at ambient temperature overnight for 18 h to allow the thiourea intermediate to form. The next86019-WO-PCT / DOW 86019 WO -37- day, copper (I) iodide (57 mg, 0.30 mmol, 0.1 equiv) and 1,10-phenanthroline (54 mg, 0.30 mmol, 0.1 equiv) were added directly as solids to the reaction mixture, followed quickly by the addition of cesium carbonate (1.96 g, 6.02 mmol, 2 equiv). The resulting heterogeneous mixture was heated to 75 °C and allowed to continue stirring at this temperature for 4 h. The mixture was then allowed to cool to ambient temperature, removed from the glovebox, diluted with ethyl acetate (250 mL), washed with water (2 x 250 mL), and then washed with brine (2 x 250 mL). The organic layer was dried over MgSO4, filtered, and concentrated to afford a pale brown residue. The material was further purified by ISCO column chromatography using 0 to 20 % gradient ethyl acetate in hexanes as the solvent system. The purified material was collected as a colorless solid. Yield: 0.59 g, 53.0 %.

[0140] 1H NMR (500 MHz, CDCl3) δ 7.53 – 7.47 (m, 1H), 7.20 (d, J = 6.1 Hz, 1H), 7.17 – 7.14 (m, 2H), 7.11 (d, J = 7.7 Hz, 1H), 7.06 (dd, J = 7.4, 1.4 Hz, 1H), 6.99 (s, 2H), 2.35 (s, 3H), 2.29 (s, 6H), 2.05 (s, 6H).13C NMR (101 MHz, CDCl3) δ 167.8, 150.9, 137.5, 137.2, 136.8, 136.6, 136.4, 131.6, 131.1, 129.0, 128.4, 128.3, 127.4, 121.5, 119.7, 21.3, 20.8, 18.2 Example 5 Ligand 3. N-(adamantyl)-4-mesitylbenzothiazol-2-amine

[0141] In a nitrogen filled glovebox, 2-bromo-6-mesityl-isothiocyanate (0.750 g, 2.26 mmol, 1 equiv), DME (10 mL), and a magnetic stir bar were added to a 20 mL glass vial. The contents were stirred at ambient temperature for 2 min, affording a colorless solution. Separately, DME (5 mL) and 1-adamantylamine (0.68 g, 4.51 mmol, 2 equiv) were combined in an 8 mL vial, affording a colorless suspension. The suspension of amine was added dropwise to the stirring solution of isothiocyanate at ambient temperature. Additional DME (2 mL) was used to quantitatively transfer all the amine reagent to the reaction vial. The resulting suspension was then allowed to continue stirring at ambient temperature overnight for 18 h to allow the thiourea intermediate to form. The next day, copper (I) iodide (43 mg, 0.23 mmol, 0.1 equiv) and 1,10- phenanthroline (41 mg, 0.23 mmol, 0.1 equiv) were added directly as solids to the reaction86019-WO-PCT / DOW 86019 WO -38- mixture, followed quickly by the addition of cesium carbonate (1.47 g, 4.51 mmol, 2 equiv). The resulting heterogeneous mixture was heated to 75 °C and allowed to continue stirring at this temperature for 4 h. The mixture was then allowed to cool to ambient temperature, removed from the glovebox, diluted with ethyl acetate (250 mL), washed with water (2 x 250 mL), and then washed with brine (2 x 250 mL). The organic layer was dried over MgSO4, filtered, and concentrated to afford a pale brown residue. The material was further purified by ISCO column chromatography using 0 to 20 % gradient ethyl acetate in hexanes as the solvent system. The purified material was collected as a colorless solid. Yield: 0.65 g, 71.4 %.

[0142] 1H NMR (400 MHz, CDCl3) δ 7.57 (dd, J = 7.7, 1.3 Hz, 1H), 7.10 (t, J = 7.6 Hz, 1H), 7.02 (dd, J = 7.4, 1.3 Hz, 1H), 6.94 (s, 2H), 5.37 (s, 1H), 2.33 (s, 3H), 2.16 – 2.07 (m, 3H), 1.99 (s, 12H), 1.75 – 1.60 (m, 6H).13C NMR (101 MHz, CDCl3) δ 163.5, 150.0, 137.0, 136.5, 136.4, 131.6, 131.5, 128.0, 127.1, 121.2, 119.2, 52.9, 42.0, 36.3, 29.6, 21.3, 20.8. Example 6 Ligand 4. N-(1-naphthyl)-4-mesitylbenzothiazol-2-amine

[0143] In a nitrogen filled glovebox, 2-bromo-6-mesityl-isothiocyanate (0.50 g, 1.50 mmol, 1 equiv), DME (8 mL), 1-naphthylamine (0.43 g, 3.01 mmol, 2 equiv), and a magnetic stir bar were combined in a 20 mL glass vial. The resulting solution was then heated to 55 °C overnight for 18 h to allow the thiourea intermediate to form. The next day, copper (I) iodide (14 mg, 0.08 mmol, 0.05 equiv) and 1,10-phenanthroline (27 mg, 0.15 mmol, 0.1 equiv) were added directly as solids to the reaction mixture, followed quickly by the addition of cesium carbonate (0.98 g, 3.01 mmol, 2 equiv). The resulting heterogeneous mixture was heated to 75 °C and allowed to continue stirring at this temperature for 20 h. The mixture was then allowed to cool to ambient temperature, removed from the glovebox, diluted with ethyl acetate (25 mL), washed with water (2 x 15 mL), and then washed with brine (2 x 10 mL). The organic layer was dried over MgSO4, filtered, and concentrated to afford a pale brown residue. The material was further86019-WO-PCT / DOW 86019 WO -39- purified by ISCO column chromatography using DCM as the solvent system. The purified material was collected as a colorless solid. Yield: 0.27 g, 45.5 %.

[0144] 1H NMR (400 MHz, CDCl3) δ 8.07 – 8.00 (m, 1H), 7.92 – 7.87 (m, 1H), 7.77 (dt, J = 8.3, 1.0 Hz, 1H), 7.71 (dd, J = 7.4, 1.1 Hz, 1H), 7.58 – 7.46 (m, 4H), 7.18 (t, J = 7.6 Hz, 1H), 7.09 (dd, J = 7.5, 1.3 Hz, 1H), 7.01 (s, 2H), 2.37 (s, 3H), 2.06 (s, 6H).13C NMR (101 MHz, CDCl3) δ 137.1, 136.6, 134.7, 128.7, 128.6, 128.3, 127.5, 126.8, 126.6, 125.9, 122.3, 121.8, 120.1, 119.9, 21.4, 20.8. Example 7 CpZrBn3

[0145] 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 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 %.86019-WO-PCT / DOW 86019 WO -40-

[0146] 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 8 nBuCpZrBn3

[0147] 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 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 %.

[0148] 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 9 Cp*ZrBn3

[0149] An adapted procedure from Organometallics, 1982,1, 793 was used. In a nitrogen filled glove box, Cp*ZrCl3(1.00 g, 3.00 mmol. 1 equiv) was combined with diethyl ether (25 mL),86019-WO-PCT / DOW 86019 WO -41- tetrahydrofuran (5 mL) and a stir bar in a 50 mL glass jar. The resulting slurry was stored in a −25 °C freezer for 60 min. Separately, a 1.0 M solution of BnMgCl in diethyl ether was added to a 20 mL glass vial and also stored in a −25 °C freezer for 60 min. After this cooling time, the Grignard solution was added dropwise to the stirring mixture of Zr precursor. Over the course of the addition the mixture turned bright yellow and remained a 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 (2 x 10 mL), affording a pale yellow solid (mixture of bright yellow product and colorless mg salts). The material was extracted into hexanes (50 mL), filtered, and concentrated to 15 mL. The bright yellow filtrate was stored at −25 °C overnight leading to the formation of yellow crystals. The crystals were collected by decanting the mother liquor, rinsing the crystals with a minimal amount of cold hexanes, and drying in vacuo. The mother liquor and hexanes wash were combined and concentrated to half the volume and then stored again in the freezer at −25 °C for a second crop that was collected in the same manner and combined with the first crop. Yield: 1.21 g, 80.6%.

[0150] 1H NMR (400 MHz, C6D6) δ 7.11 (t, J = 7.7 Hz, 6H), 6.99 – 6.94 (m, 3H), 6.60 – 6.53 (m, 6H), 1.70 (s, 15H), 1.66 (s, 6H).13C NMR (101 MHz, C6D6) δ 144.5, 129.5, 128.6, 123.3, 119.7, 70.7, 11.7. Example 10 MeCpZrBn3

[0151] 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 toluene86019-WO-PCT / DOW 86019 WO -42- (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%.

[0152] 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. Example 11 Procatalyst 1

[0153] In a nitrogen filled glovebox, N-(2,6-dimethylphenyl)-4-mesitylbenzothiazol-2-amine (80 mg, 0.215 mmol, 1 equiv) was combined with toluene (2 mL) and a magnetic stir bar in a 7 mL vial, affording a homogeneous colorless solution after 2 - 3 min of stirring. In a separate 20 mL scintillation vial, CpZrBn3 (90 mg, 0.210 mmol, 0.98 equiv) was combined with toluene (6 mL) and a magnetic stir bar, and this mixture was stirred at room temperature until a homogenous yellow solution was achieved (~ 3 min). The colorless solution of benzothiazole was added dropwise to the yellow solution of CpZrBn3 while gently stirring at room temperature. No obvious color changes occurred upon addition of the ligand, besides a very slight decrease in intensity of the pale yellow as more drops of ligand solution were added. Additional toluene (1 mL) was used to ensure quantitative transfer of the ligand material into the reaction vial. The pale-yellow reaction mixture was left to stir a room temperature overnight in the glovebox for approximately 16 h. The next day, the pale yellow reaction mixture was concentrated under reduced pressure and then triturated with hexanes (2 x 4 mL). The complex was obtained as a pale yellow solid. Yield: 0.144 g, 94.4%.

[0154] 1H NMR (500 MHz, C6D6) δ 7.21 – 7.14 (overlapping with NMR solvent), 7.11 (dd, J = 7.7, 1.5 Hz, 1H), 6.93 – 6.91 (overlapping resonances, 4H), 6.89 – 6.83 (overlapping resonances,86019-WO-PCT / DOW 86019 WO -43- 5H), 6.70 (d, J = 7.5 Hz, 4H), 5.48 (s, 5H), 2.32 (d, J = 11.1 Hz, 2H), 2.30 (s, 3H), 2.16 (d, J = 10.5 Hz, 2H), 2.14 (s, 6H), 1.89 (s, 6H).13C NMR (126 MHz, C6D6) δ 179.6, 150.7, 148.9, 148.4, 137.5, 137.3, 137.3, 130.7, 130.1, 129.8, 129.6, 129.3, 129.2, 128.8, 128.6, 126.3, 125.7, 125.6, 125.4, 122.4, 121.6, 120.5, 114.7, 72.0, 21.4, 21.3. Example 12 Procatalyst 2

[0155] In a nitrogen filled glovebox, N-phenyl-4-mesityl-benzothiazol-2-amine (150 mg, 0.435 mmol, 1 equiv) was combined with toluene (3 mL) and a magnetic stir bar in a 7 mL screw cap vial, affording a homogeneous colorless solution after 2 - 3 min of stirring. In a separate 20 mL scintillation vial, CpZrBn3 (183 mg, 0.427 mmol, 0.98 equiv) was combined with toluene (12 mL) and a small magnetic stir bar, and this mixture was stirred at room temperature until a homogenous yellow solution was achieved (~ 5 min). The colorless solution of benzothiazole was added dropwise to the yellow solution of CpZrBn3 while gently stirring at room temperature. Additional toluene (1 mL) was used to ensure quantitative transfer of the ligand material into the reaction vial. The pale yellow homogeneous reaction mixture was left to stir at ambient temperature overnight in the glovebox for approximately 16 h. The next day, the volatiles were removed under reduced pressure, affording a yellow residue that was then triturated with hexanes (2 x 4 mL). The complex was obtained as a pale yellow solid. Yield: 0.286 g, 96.3 %.

[0156] 1H NMR (500 MHz, C6D6) δ 7.20 – 7.11 (overlapping with NMR solvent), 7.06 (t, J = 7.9 Hz, 2H), 6.94 – 6.81 (overlapping resonances, 5H), 6.84 (s, 2H), 6.68 (d, J = 7.6 Hz, 4H), 6.63 – 6.60 (m, 2H), 5.51 (s, 5H), 2.30 (d, J = 10.3 Hz, 2H), 2.25 (s, 3H), 2.17 (s, 6H), 2.10 (d, J = 10.5 Hz, 2H).13C NMR (126 MHz, C6D6) δ 179.6, 150.7, 148.9, 148.4, 137.5, 137.3, 137.3, 130.7, 130.1, 129.8, 129.6, 129.3, 129.2, 128.8, 128.6, 126.3, 125.7, 125.6, 125.4, 122.4, 121.6, 120.5, 114.7, 72.0, 21.4, 21.3.86019-WO-PCT / DOW 86019 WO -44- Example 13 Procatalyst 3

[0157] In a nitrogen filled glovebox, N-phenyl-4-mesityl-benzothiazol-2-amine (100 mg, 0.29 mmol, 1 equiv) was combined with toluene (4 mL) in an 8 mL vial, affording a colorless solution. Separately,nBuCpZrBn3(141 mg, 0.29 mmol, 1 equiv) was combined with toluene (4 mL) and a small magnetic stir bar. The resulting pale orange-yellow solution ofnBuCpZrBn3 was gently stirred at room temperature while the colorless solution of benzothiazole was added dropwise. No obvious color changes occurred upon addition of the ligand, besides a very slight decrease in intensity of the pale orange-yellow as more drops of ligand solution were added. An additional 2 mL of toluene was used to quantitatively transfer all the ligand into the reaction vial. The reaction mixture was then allowed to continue stirring at room temperature in the glovebox for another 16 h. The next day, the reaction mixture appeared the same with no changes in color or turbidity. The reaction mixture was concentrated under reduced pressure and then triturated with hexanes (3 x 3 mL). The complex was obtained as a yellow-orange solid. Yield: 0.213 g, 99.4 %.

[0158] 1H NMR (500 MHz, C6D6) δ 7.24 – 7.17 (overlapping with NMR solvent), 7.13 – 7.08 (m, 2H), 6.96 – 6.86 (overlapping resonances, 5H), 6.85 (s, 2H), 6.80 – 6.73 (overlapping, 6H), 5.65 (t, J = 2.7 Hz, 2H), 5.52 (t, J = 2.7 Hz, 2H), 2.36 (d, J = 10.4 Hz, 2H), 2.26 (s, 3H), 2.16 (s, 6H), 2.07 (d, J = 10.5 Hz, 2H), 1.89 – 1.81 (m, 2H), 1.17 – 1.00 (overlapping resonances, 4H), 0.72 (t, J = 7.2 Hz, 3H).13C NMR (126 MHz, C6D6) δ 179.6, 150.7, 149.1, 149.1, 137.4, 137.4, 137.3, 131.4, 130.7, 130.0, 129.9, 129.6, 129.2, 128.7, 126.4, 125.9, 125.8, 122.4, 121.7, 120.5, 116.0, 113.4, 73.2, 33.5, 28.3, 22.6, 21.4, 21.3, 13.9.86019-WO-PCT / DOW 86019 WO -45- Example 14 Procatalyst 4

[0159] In a nitrogen filled glovebox, N-(2,6-dimethylphenyl)-4-mesitylbenzothiazol-2-amine (100 mg, 0.268 mmol, 1 equiv) was combined with toluene (4 mL) in a 7 mL glass vial, affording a colorless solution. Separately,nBuCpZrBn3(130 mg, 0.268 mmol, 1 equiv) was combined with toluene (4 mL) and a small magnetic stir. The resulting pale orange-yellow solution ofnBuCpZrBn3 was gently stirred at room temperature while the colorless solution of benzothiazole was added dropwise. No obvious color changes occurred upon addition of the ligand, besides a very slight decrease in intensity of the pale orange-yellow color as more drops of ligand solution were added. An additional 2 mL of toluene was used to quantitatively transfer all the ligand into the reaction vial. The reaction mixture was then allowed to continue stirring at room temperature in the glovebox for another 16 h. The next day, the reaction mixture appeared the same with no changes in color or turbidity. The reaction mixture was concentrated under reduced pressure and then triturated with hexanes (2 x 2 mL). The complex was obtained as a yellow-orange solid. Yield: 0.200 g, 97.2 %.

[0160] 1H NMR (500 MHz, C6D6) δ 7.21 – 7.16 (overlapping with NMR solvent), 6.99 – 6.92 (overlapping resonances, 4H), 6.90 – 6.85 (overlapping resonances, 5H), 6.76 (d, J = 7.6 Hz, 4H), 5.55 (t, J = 2.7 Hz, 2H), 5.48 (t, J = 2.6 Hz, 2H), 2.39 (d, J = 10.5 Hz, 2H), 2.30 (s, 3H), 2.21 (d, J = 10.5 Hz, 2H), 2.16 (s, 6H), 1.99 (s, 6H), 1.82 – 1.77 (m, 2H), 1.18 – 0.96 (overlapping resonances, 4H), 0.69 (t, J = 7.1 Hz, 3H).13C NMR (126 MHz, C6D6) δ 179.3, 150.0, 149.3, 147.8, 137.5, 137.5, 137.3, 133.6, 131.9, 130.8, 130.1, 129.6, 129.4, 129.1, 128.6, 126.8, 125.6, 122.2, 121.6, 120.5, 115.9, 113.8, 74.1, 33.9, 28.2, 22.5, 21.4, 21.3, 18.5, 13.8.86019-WO-PCT / DOW 86019 WO -46- Example 15 Procatalyst 5

[0161] In a nitrogen filled glovebox, a ~1 mL aliquot from a 5 mM toluene solution N- (adamantyl)-4-mesitylbenzothiazol-2-amine was transferred to a 7 mL glass vial and the volatiles were removed in vacuo. The resulting residue was massed and then 1 equiv of a 5 mM C6D6solution of metal precursornBuCpZrBn3was added to the vial at room temperature. The mixture was transferred to an NMR tube and monitored by1H NMR spectroscopy to ensure conversion to the target complex. Conversion was determined by the appearance of one equivalent of toluene. The sample was returned to the glovebox and all volatiles were removed in vacuo and triturated with hexanes (2 x 1 mL). The material obtained after removal of the volatiles was used without further purification.

[0162] 1H NMR (500 MHz, C6D6) δ 7.28 (dd, J = 5.4, 3.7 Hz, 1H), 7.19 – 7.08 (overlapping with NMR solvent), 7.03 – 6.96 (overlapping resonances, 8H), 6.91 – 6.87 (overlapping resonances, 3H), 6.85 (t, J = 7.3 Hz, 2H), 6.03 (t, J = 2.7 Hz, 2H), 5.92 (t, J = 2.7 Hz, 2H), 2.38 (d, J = 11.8 Hz, 2H), 2.32 (s, 3H), 2.19 (t, J = 7.6 Hz, 2H), 2.08 (s, 6H), 1.98 – 1.89 (br s, 3H), 1.78 (d, J = 11.7 Hz, 2H), 1.68 – 1.63 (m, 6H), 1.56 – 1.49 (overlapping resonances, 6H), 1.40 (p, J = 7.6 Hz, 2H), 1.22 (p, J = 7.4 Hz, 2H), 0.83 (t, J = 7.3 Hz, 3H).86019-WO-PCT / DOW 86019 WO -47- Example 16 Procatalyst 6

[0163] In a nitrogen filled glovebox, N-(adamantyl)-4-mesitylbenzothiazol-2-amine (50 mg, 0.124 mmol, 1 equiv) was dissolved in toluene (4 mL) in a glass vial. Separately, CpZrBn3 (53 mg, 0.124 mmol, 1 equiv) was combined with toluene (4 mL) and a magnetic stir bar in a 20 mL glass vial. The benzothiazole solution was then added dropwise to the stirring solution of yellow CpZrBn3 resulting in a resulting in a slight color change to pale yellow. Additional toluene (1 mL) was used to ensure quantitative transfer of the ligand material into the reaction vial. The mixture was stirred for an additional 16 h at room temperature and no further color or turbidity changes were observed. The next day, the volatiles were removed in vacuo and the yellow residue was triturated with hexanes (2 x 2 mL) and dried. The complex was obtained as a yellow solid. Yield: 0.089 g, 96.8 %.

[0164] 1H NMR (500 MHz, C6D6) δ 7.28 (dd, J = 6.3, 2.8 Hz, 1H), 7.18 – 7.10 (overlapping with NMR solvent), 6.97 (s, 2H), 6.90 – 6.80 (overlapping resonances, 8H), 6.00 (s, 5H), 2.30 (s, 3H), 2.08 (d, J = 11.4 Hz, 2H), 2.04 (s, 6H), 2.02 (d, J = 11.9 Hz, 2H), 1.93 (s, 3H), 1.82 – 1.73 (m, 6H), 1.54 (q, J = 12.2 Hz, 6H).13C NMR (126 MHz, C6D6) δ 170.3, 162.8, 151.7, 151.4, 146.8, 137.9, 137.8, 137.6, 137.5, 137.2, 136.6, 136.2, 132.7, 132.0, 131.9, 129.9, 129.6, 129.3, 129.2, 128.6, 127.5, 125.7, 125.7, 121.9, 121.8, 121.5, 120.0, 119.4, 115.7, 77.6, 56.5, 53.5, 41.8, 40.9, 36.5, 36.4, 30.1, 29.9, 21.4, 21.3, 21.2, 21.2, 21.1.86019-WO-PCT / DOW 86019 WO -48- Example 17 Procatalyst 7

[0165] In a nitrogen filled glovebox, N-(1-naphthyl)-4-mesitylbenzothiazol-2-amine (66 mg, 0.17 mmol, 1.02 equiv) and toluene (2 mL) were combined in a 7 mL vial, affording a pale peach solution. In a separate 20 mL scintillation vial, CpZrBn3(70 mg, 0.16 mmol, 1 equiv), toluene (3 mL), and a stir bar were combined. The solution of benzothiazole was added dropwise at room temperature to the bright yellow solution of Zr precursor, resulting in a slight color change to pale yellow. Additional toluene (1 mL) was used to ensure quantitative transfer of the ligand material into the reaction vial. The mixture was stirred for an additional 16 h at room temperature and no further color or turbidity changes were observed. The next day, the volatiles were removed in vacuo and the yellow residue was triturated with hexanes (2 x 2 mL) and dried. The complex was obtained as a yellow solid.Yield: 0.118 g, 98.9%.1H NMR (400 MHz, C6D6) δ 7.68 – 7.57 (m, 2H), 7.49 – 7.44 (m, 1H), 7.27 – 7.22 (m, 2H), 7.21 – 7.14 (overlapping with NMR solvent), 7.07 (dd, J = 7.7, 1.5 Hz, 1H), 6.97 – 6.83 (m, 6H), 6.78 – 6.74 (m, 4H), 6.69 (dd, J = 7.3, 1.2 Hz, 1H), 5.41 (s, 5H), 2.47 (d, J = 9.7 Hz, 2H), 2.27 (s, 3H), 2.24 - 2.21 (overlapping resonances, 8H).13C NMR (101 MHz, C6D6) δ 180.2, 148.9, 147.1, 137.5, 137.4, 135.3, 130.8, 130.3, 129.6, 129.5, 129.2, 128.9, 127.2, 127.1, 126.8, 126.4, 125.6, 123.2, 122.5, 122.5, 121.6, 120.6, 114.8, 21.5, 21.3.86019-WO-PCT / DOW 86019 WO -49- Example 18 Procatalyst 8

[0166] In a nitrogen filled glovebox, N-(1-naphthyl)-4-mesitylbenzothiazol-2-amine (50 mg, 0.13 mmol, 1.02 equiv) and toluene (1 mL) were combined in a 7 mL vial, affording a pale peach solution. Separately,nBuCpZrBn3(60 mg, 0.12 mmol, 1 equiv), toluene (2 mL), and a stir bar were combined in a 20 mL glas vial. The solution of benzothiazole was added dropwise at room temperature to the golden-yellow solution of Zr precursor, resulting in a slight decrease in golden- yellow color intensity. The mixture was stirred for an additional 16 h at room temperature and no additional color or turbidity changes were observed. The volatiles were removed in vacuo and the golden-yellow residue was triturated with hexanes (2 x 2 mL) and dried under vacuum. The resulting golden-yellow solid was extracted into pentane (4 mL), filtered, and concentrated to ~2 mL. The filtrate was stored at −25 °C to induce crystallization. The next day, precipitate was isolated by decanting the mother liquor and drying the solid in vacuo. The complex was obtained as a golden yellow solid and was stored at −25 °C. Yield: 0.076 g, 78.1 %. VT1H NMR characterization at 60 °C (330 K) allows for improved peak resolution.

[0167] 1H NMR (400 MHz, C6D6, 330 K) δ 7.82 – 7.70 (m, 1H), 7.62 (dd, J = 7.4, 2.1 Hz, 1H), 7.50 (d, J = 8.2 Hz, 1H), 7.29 – 7.22 (m, 2H), 7.22 – 7.14 (overlapping with NMR solvent), 6.99 – 6.84 (m, 8H), 6.82 (d, J = 7.6 Hz, 4H), 5.60 – 5.49 (br m, 2H), 5.45 (t, J = 2.7 Hz, 2H), 2.50 (d, J = 10.4 Hz, 2H), 2.27 (s, 3H), 2.21 – 2.13 (overlapping resonances, 8H), 1.85 (t, J = 7.3 Hz, 2H), 1.10 – 0.90 (overlapping resonances, 4H), 0.65 (t, J = 7.0 Hz, 3H).13C NMR (101 MHz, C6D6) δ 180.3, 149.0, 149.0, 147.1, 137.5, 137.4, 135.4, 131.4, 130.9, 130.4, 129.7, 129.1, 128.9, 128.8, 127.2, 127.1, 126.8, 126.2, 125.9, 123.5, 122.9, 122.4, 121.7, 120.6, 115.9, 113.4, 33.5, 28.4, 22.5, 21.5, 21.3, 13.8.86019-WO-PCT / DOW 86019 WO -50- Example 19 Procatalyst 9

[0168] In a nitrogen filled glovebox, N-(2,6-dimethylphenyl)-4-mesitylbenzothiazol-2-amine (56 mg, 0.15 mmol, 1.02 equiv) and C6D6 (0.4 mL) were combined in a 7 mL glass vial, affording a colorless solution. Separately,MeCpZrBn3(65 mg, 0.15 mmol, 1 equiv), a stir bar, and C6D6(0.4 mL) were combined in a 7 mL glass vial, affording a golden colored solution. The solution of benzothiazole was then added dropwise to the stirring solution of Zr precursor at room temperature, causing the mixture to become less intense in color. An additional 0.2 mL of C6D6 was used to quantitatively transfer all the ligand into the reaction vial. The resulting golden colored reaction mixture was allowed to stir at room temperature for 20 h. The next day, the volatiles were removed in vacuo, affording a golden colored residue that was then triturated with hexanes (2 x 2 mL). The resulting golden yellow solid was washed with a small amount of cold pentane (2 x 0.5 mL) and then dried under vacuum. The complex was obtained as a yellow solid. Yield: 0.082 g, 77.3 %.

[0169] 1H NMR (400 MHz, C6D6) δ 7.23 – 7.09 (overlapping with NMR solvent), 6.95 – 6.90 (overlapping resonances, 4H), 6.93 – 6.84 (m, 5H), 6.74 (d, J = 7.3 Hz, 4H), 5.46 (t, J = 2.6 Hz, 2H), 5.43 (t, J = 2.6 Hz, 2H), 2.38 (d, J = 10.5 Hz, 2H), 2.30 (s, 3H), 2.19 (d, J = 10.4 Hz, 2H), 2.15 (s, 6H), 1.96 (s, 6H), 1.44 (s, 3H).13C NMR (101 MHz, C6D6) δ 179.3, 149.9, 149.2, 147.8, 137.5, 137.5, 137.3, 133.6, 130.8, 130.0, 129.6, 129.4, 129.1, 128.6, 126.8, 126.4, 125.6, 122.2, 121.6, 120.5, 116.7, 113.8, 73.9, 21.4, 21.3, 18.5, 13.4.86019-WO-PCT / DOW 86019 WO -51- Example 20 Procatalyst 10

[0170] In a nitrogen filled glovebox, N-phenyl-4-mesityl-benzothiazol-2-amine (50 mg, 0.14 mmol, 1 equiv) was combined with toluene (4 mL) in an 8 mL vial, affording a colorless solution. Separately, Cp*ZrBn3(72 mg, 0.14 mmol, 1 equiv) was combined with toluene (4 mL) and a small magnetic stir bar. The resulting bright yellow solution of Cp*ZrBn3 was gently stirred at room temperature while the colorless solution of benzothiazole was added dropwise. No obvious color changes occurred upon addition of the ligand, besides a very slight decrease in intensity of the yellow color as more drops of ligand solution were added. An additional 1 mL of toluene was used to quantitatively transfer all the ligand into the reaction vial. The reaction mixture was then heated at 50 C in the glovebox for 4 h. The reaction mixture was allowed to cool to ambient temperature and then concentrated under reduced pressure. The yellow residue was then triturated with hexanes (3 x 3 mL). The complex was obtained as a yellow solid. Yield: 0.098 g, 90.4 %.

[0171] 1H NMR (400 MHz, C6D6) δ 7.15 – 7.00 (overlapping resonances, 13H), 6.93 – 6.82 (overlapping resonances, 7H), 2.35 (d, J = 12.2 Hz, 2H), 2.26 (s, 3H), 2.10 (s, 6H), 1.71 (d, J = 12.3 Hz, 2H), 1.67 (s, 15H).13C NMR (101 MHz, C6D6) δ 174.7, 149.0, 137.4, 137.2, 131.0, 130.7, 130.1, 129.4, 129.3, 127.3, 124.8, 123.4, 122.7, 122.6, 122.2, 120.5, 79.2, 21.5, 21.2, 11.5. Example 21 Polymerization Reactions

[0172] Catalyst activity (in terms of quench time and polymer yield) and resulting polymer characteristics were assessed for Procatalysts 1 − 10. The polymerization reactions were carried out in a parallel pressure reactor (PPR) and semi-batch reactor.86019-WO-PCT / DOW 86019 WO -52-

[0173] The reaction conditions for the results tabulated in Table 1 followed the General Procedure for PPR Screening Experiments disclosed herein. TABLE 1: PPR data (averaged over duplicate runs) for various 2-amino-thiazole ligand / group IV cyclopentadienyl supported metal precursor pairs.(comparative) ,

[0174] The reaction conditions for the results tabulated in Table 2 is as follows: The standard ethylene-octene copolymerization semi-batch reactor conditions of the results in Table 2 for polymerization reaction at 120 °C include 46.3 g of ethylene, 302 g of 1-octene, 612 g of Isopar E, 1.2 eq. of RIBS-2 activator with respect to catalyst, 10 umol 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 umol of MMAO-3A, 327 psi reactor pressure. The standard ethylene-octene copolymerization semi-batch reactor conditions of the results in Table 2 for polymerization reaction at 190 °C include 43 g of ethylene, 301 g of 1-octene, 520 g of Isopar E, 1.2 eq. of RIBS-2 activator with respect to catalyst, 10 umol of MMAO-3A, 400 psi reactor pressure.86019-WO-PCT / DOW 86019 WO -53- TABLE 2: Semi-batch reactor results for ethylene-octene copolymerization data for a series of heteroleptic 2-amino-thiazole supported cyclopentadienyl complexes (Procatalysts 1-10).n.d. = not determined86019-WO-PCT / DOW 86019 WO -54- Comparative metal-ligand complexes

[0175] CMLC-1 was prepared according to WO2020263790. CMLC-2 was prepared according to WO2020263790. CMLC-3 was prepared according to the synthesis ofnBuCpZrBn3 (Example 8).

[0176] The standard ethylene-octene copolymerization semi-batch reactor conditions of the results in Table 3 for polymerization reaction at 120 °C include 46.3 g of ethylene, 302 g of 1-octene, 612 g of Isopar E, 1.2 eq. of RIBS-2 activator with respect to catalyst, 10 umol of MMAO-3A, 290 psi reactor pressure. The standard ethylene-octene copolymerization semi-batch reactor conditions of the results in Table 3 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 3: Ethylene-octene copolymerization data for comparative metal ligand complexes (CMLCs) and relevant heteroleptic 2-amino-thiazole complexes (Procatalysts).86019-WO-PCT / DOW 86019 WO -55-

[0177] As shown in the PPR data presented in Table 1 (IE1 – IE6) and the batch reactor data in Table 2 and Table 3 (IE7 – IE33), utilizing heteroleptic group IV cyclopentadienyl complexes bearing 2-amino-thiazole ligands with various substituents according to the embodiments described herein provide improved performance of catalyst systems and / or achieve different desired polymer properties, such as lower weight average molecular weight and / or significantly lower comonomer incorporation. For instance, such catalyst systems may provide improved efficiency at elevated temperatures, such as temperatures greater than or equal to 120 ºC.

[0178] Under the conditions of the polymerization experiments at 120 °C and 150 °C, the efficiency of the procatalysts in IE7 – IE8, IE12 – IE13, IE15 – IE16, IE19 – IE20, IE22 – IE23, IE25 – IE26, and IE28 – IE29 were greater than or equal to 280,000 g poly / g metal. The procatalysts in IE9, IE14, and IE30 were also evaluated at 190 °C, and demonstrated efficiencies greater than 130,000 g poly / g metal at this elevated temperature.86019-WO-PCT / DOW 86019 WO -56-

[0179] As shown in Table 3, using Procatalyst 6, which is a group IV cyclopentadienyl complex bearing an adamantyl-substituted 2-amino-thiazole ligand, resulted in efficiencies of 680,000 and 620,000 g poly / g metal, under polymerization conditions at 120 °C (IE19) and 150 °C (IE20) respectively, both of which are higher than the efficiencies observed for the comparative procatalyst, CMLC-1, whose efficiencies were 470,000 and 310,000 g poly / g metal at 120 °C (CE4) and 150 °C (CE5), respectively. Moreover, Procatalyst 6, produces polymer with much lower molecular weights under 120 °C (IE19) and 150 °C (IE20) reactor conditions (46,000 and 27,000 g / mol, respectively) and much lower 1-octene incorporation (1.6 and 2.0 mol% C8, respectively) compared to that of the comparative procatalyst CMLC-1 which produced polymer having molecular weights of 820,000 and 410,000 g / mol at 120 °C (CE4) and 150 °C (CE5), respectively and 1-octene incorporation of 10.6 and 8.4 mol% at 120 °C and 150 °C, respectively.

[0180] As shown in Table 3, using Procatalysts 2, 3, and 10, each of which are heteroleptic cyclopentadienyl group IV complexes bearing one phenyl-substituted 2-amino-thiazole ligand, under polymerization conditions at 120 °C (IE10, IE12, and IE31) and 150 °C (IE11, IE13, and IE32) produced polymer with lower 1-octene incorporation than the comparative procatalyst CMLC-2 (CE6 and CE7). Moreover, at 150 °C (IE11, IE13, and IE32) Procatalysts 2, 3, and 10 all produced polymer with lower molecular weights (77,000, 47,000, and 89,000 g / mol, respectively) than CMLC-2 in CE7 (98,000 g / mol).

[0181] Also shown in Table 3, in comparison to an n-butyl-cyclopentadienyl zirconium tribenzyl complex (CMLC-3), using Procatalysts 3, 4, and 8, each of which bear a 2-amino- thiazole ligand in their coordination sphere, demonstrate lower 1-octene incorporation, lower molecular weight capabilities, and narrower polydispersities at both 120 °C (IE12, IE15, IE25 vs CE8) and 150 °C (IE13, IE16, IE26 vs CE9).

[0182] Improved activity was observed for those procatalysts possessing an ortho-substituted aryl amine group on the 2-benzothiazole position such as, but not limited to, 2,6-dimethylphenyl and 1-naphthyl (Procatalysts 1, 4, 8, and 9). In addition, high activity was observed for the procatalysts that included cyclopentadienyl ligands bearing mono-methyl and mono-n-butyl substitution (Procatalysts 3, 4, 8, and 9).

[0183] Moreover, based on the GPC analysis of the polyethylene-octene copolymers produced, under these solution process conditions at 120 °C and 150 °C (Table 2), several of the procatalysts86019-WO-PCT / DOW 86019 WO -57- produced polyethylene with very low octene incorporation (0.0 – 2.0 mol%), as seen in IE7-9, IE12-13, IE15-16, IE19-20, IE22-26, and IE28-30. Furthermore, all procatalysts produced polymer with lower octene incorporation compared to CMLC-1 (CE4-CE5; 8.4 – 10.6 mol%). The procatalysts that produced polymer with the lowest 1-octene incorporation were those bearing a 2,6-dimethylphenyl N-aryl substituent on the 2-amino-benzimidazole ligand, namely Procatalysts 1, 4, and 9 (IE7-9, IE15-16, and IE28-30). At all the reactor temperatures in these polymerization studies, Procatalysts 1, 4, and 9 produced polymer with less than or equal to 1 mol% octene. Importantly, these procatalysts also produce polymer with a range of Mwthat trends with the identity of the N-aryl amine. That is, the Mwof the polymer may be tuned by selection of the procatalyst.

[0184] The high activity of these procatalysts combined with their ability to produce low molecular weight, low octene content polymer that is tunable with different substitution patterns on the overall catalyst framework, offers a resin with potentially advantageous properties for both single and multi-catalyst applications using single and / or multi-reactor configurations over conventional catalyst systems.

Claims

1. 86019-WO-PCT / DOW 86019 WO -58- 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 +3 or +4; each X is a monodentate or bidentate ligand independently chosen 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 RXis independently selected from a (C1−C30)hydrocarbyl (C1−C30)heterohydrocarbyl, (C6-C30)aryl, and (C3-C30)heteroaryl; n is 1 or 2; each of R8−R12is independently selected from (C1–C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, ^Si(RC)3, –Ge(RC)3, and –H, wherein optionally, any of R8-R12are covalently connected to form one or more ring or multi-ring structures. R1is (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C6-C30)aryl, or (C3- C30)heteroaryl; each of R2and R3is 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 R2and R3are optionally covalently linked to form an aromatic ring or a non- aromatic ring; and each RCis independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3- C30)heteroaryl, and –H.86019-WO-PCT / DOW 86019 WO -59- 2. The catalyst system according to claim 1, wherein: each X is independently selected from (C1−C10)alkyl, (C6^C20)aryl, and halogen; and R1is a (C1−C30)alkyl or a (C6−C30)aryl.

3. The catalyst system of any preceding claim, wherein R2and R3are covalently linked to form an aromatic ring, and the procatalyst has a structure according to Formula (II):where each R1, R8−R12, X, n, and M are defined as in Formula (I); and each R4, R5, R6, and R7is independently (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, (C6-C40)aryl, (C3-C40)heteroaryl, a halogen, or –H .

4. The catalyst system of claim 3, wherein R4is (C6−C40)aryl or (C3−C40)heteroaryl.

5. The catalyst system of claim 3, wherein R4is 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 R7are −H.

7. The catalyst system of any preceding claim, wherein R1is (C6−C30)aryl.

8. The catalyst system of any preceding claim, wherein R1is unsubstituted phenyl, substituted phenyl, unsubstituted anthracenyl, substituted anthracenyl, unsubstituted naphthyl, or substituted naphthyl.

9. The catalyst system of any preceding claim, wherein R1is 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.

10. The catalyst system of any one of claims 1–6, wherein R1is (C1−C12)alkyl, (C1−C12)cycloalkyl, trimethylsilyl methyl, benzyl, or 1-adamantyl.86019-WO-PCT / DOW 86019 WO -60- 11. The catalyst system of any preceding claim, wherein each X is independently selected from methyl, benzyl, phenyl, trimethylsilyl methyl, and chloro.

12. The catalyst system of any preceding claim, wherein: each of R8−R11is –H and R12is (C1−C10)alkyl, (C6^C20)aryl, (C1−C20)heterohydrocarbyl, ^Si(RC)3, or ^Ge(RC)3; or each of R8−R11is –H and R12is (C1−C10)alkyl or (C6^C20)aryl.

13. The catalyst system of any preceding claim, wherein the procatalyst has a structure according to any one of formulas:Procatalyst 3 Procatalyst 486019-WO-PCT / DOW 86019 WO -61-14. 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.

15. A method of making an ethylene-based polymer comprising polymerizing ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of the catalyst system of any one of the preceding claims, wherein the polymerizing comprises solution polymerization.

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