Slurry phase polymerization processes for making ethylene-based polymer using catalyst systems containing 2-amino-thiazoles

Abstract

A method of making polyethylene comprises: polymerizing in a slurry phase reactor ethylene monomer and optionally at least one C3 to C20 1-alkene comonomer in the presence of a suspension comprising a catalyst system in an inert hydrocarbon liquid, the catalyst system comprising a procatalyst complex having a structure according to formula (I).

Description

86020-WO-PCT / DOW 86020 WO SLURRY PHASE POLYMERIZATION PROCESSES FOR MAKING ETHYLENE- BASED POLYMER USING CATALYST SYSTEMS CONTAINING 2-AMINO- THIAZOLES CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 665,777 filed June 28, 2024, the entire disclosure of which is hereby incorporated by reference. BACKGROUND

[0002] Polyethylene is manufactured for a wide variety of articles. The polyethylene and polypropylene polymerization process can be varied in a number of respects to produce awide variety of resultant polyethylene resins having different physical properties tha t renderthe various resins suitable for use in different applications. Polyethylene is produced via various catalyst systems. Selection of such catalyst systems used in the polymerization process of the polyethylene is an important factor contributing to the characteristics and properties of the polyethylene. BRIEF SUMMARY

[0003] Despite previous research efforts in developing catalyst systems suitable for polyethylene polymerization, there is still a need to increase the efficiencies of catalyst systems to reduce their cost-in-use, particularly without compromising other critical properties such as the weight average molecular weight of the polymer as formed, before any blending with other polymers, and comonomer incorporation. These polyethylene polymers may be utilized for a number of products including films, fibers, pipes, nonwoven and / or woven fabrics, extruded articles, and / or molded articles, among others. There is continued focus in the industry on developing new and improved materials and / or processes that may be utilized to form these polymers. Embodiments of the present disclosure meet this need by providing methods of making polyethylene in a slurry phase polymerization reactor, which utilize a catalyst system comprising a procatalyst as described further herein. These methods of making polyethylene result in high productivity and / or efficiency across a variety of polyethylene applications, including making linear-low to high density polyethylenes,86020-WO-PCT / DOW 86020 WO polyethylenes having fractional melt indices, desirable melt flow properties, ultra-low comonomer consumption or high ethylene selectivity, and / or broad molecular weight distributions. These features make these catalysts amenable to making bi- and multi-modal resins with additional degrees of freedom in designs for single and multi-catalyst applications for single and / or multi-reactor processes, which can improve the end resin / product performance.

[0004] Embodiments of the present disclosure are directed to methods of making polyethylene comprising: polymerizing, in a slurry phase polymerization reactor, ethylene monomer and optionally at least one C3to C201-alkene comonomer in the presence of a suspension comprising a catalyst system in an inert hydrocarbon liquid, the catalyst systemcomprising a supported procatalyst complex having a structure according to Formula (I):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 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; Q is a monoanionic spectator ligand selected from (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C5-C30)aryl, and (C3-C30)heteroaryl, wherein Q is different from each X; 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 to86020-WO-PCT / DOW 86020 WO form an aromatic ring or a non-aromatic ring, each RCis independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3- C30)heteroaryl, and –H.

[0005] These and other embodiments are described in more detail in the Detailed Description. It is to be understood that both the foregoing general description and the following detailed description present embodiments of the presently disclosed technology, and are intended to provide an overview or framework for understanding the nature and character of the technology as it is claimed. DETAILED DESCRIPTION

[0006] Common abbreviations are listed below:

[0007] 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; MgSO4: 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; tBu3PN-SiMe3: 1,1,1-tri(tert-butyl)-N-trimethylsilyl-λ5- phosphanimine; CpZrBn3: cyclopentadienylzirconium(IV) tribenzyl; nBuCpZrBn3: n- butylcyclopentadienylzirconium(IV) tribenzyl; Cp*ZrBn3: pentamethylcyclopentadienylzirconium(IV) tribenzyl; MeCpZrBn3: methylcyclopentadienylzirconium(IV) tribenzyl; CpHfBn3: cyclopentadienylhafnium(IV) tribenzyl; MeCpHfBn3: methylcyclopentadienylhafnium(IV) tribenzyl ; IPrNZrBn3: 1,3- bis(2,6-diisopropylphenyl)imidazol-2-ylidenezirconium(IV) tribenzyl; tBuNHfBn3: 1,3- di(tert-butyl)imidazol-2-ylidenehafnium(IV) tribenzyl; tBuNZrBn3: 1,3-di(tert- butyl)imidazol-2-ylidenezirconium(IV) tribenzyl; (Me2N)TiCl3: dimethylamidotitanium(IV) trichloride (IMesN)TiCl3(HNMe2): 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-86020-WO-PCT / DOW 86020 WO ylidenetitanium(IV) trichloride dimethylamine adduct; (IMesN)TiMe3: 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidenetitanium(IV) trimethyl; Cy3PNZrBn3: tricyclohexyl- phosphinimideziconium(IV) tribenzyl; tBu3PNTiCl3 : tri(tert- butyl)phosphinimidetitanium(IV) trichloride; tBu3PNTiMe3 : tri(tert- butyl)phosphinimidetitanium(IV) trimethyl; N2: nitrogen gas; PhMe: toluene; PPR : parallel pressure reactor; MAO : methylaluminoxane; MMAO : modified methylaluminoxane; GC : gas chromatography; LC : liquid chromatography; 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.

[0008] 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 reactswith a procatalyst in a manner that converts the procatalyst to a catalytically active catalyst.As used herein, the terms “activating co-catalyst” and “activator” are interchangeable terms.

[0009] 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.

[0010] 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.

[0011] The term “polymer” refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term “polymer” thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer” which refers to polymers prepared from two or more different monomer types.86020-WO-PCT / DOW 86020 WO

[0012] “Polyethylene” or “ethylene-based polymer” refers to polymers comprising greater than 50% by weight derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more monomer types). Common forms of polyethylene known in the art include Low-density polyethylene (LDPE); Linear Low-density polyethylene (LLDPE); Ultra Low-density polyethylene (ULDPE); Very Low-density polyethylene (VLDPE); single-site catalyzed Linear Low-density polyethylene, including both linear and substantially linear low-density resins (m-LLDPE); MediumDensity Polyethylene (MDPE); and High Density Polyethylene (HDPE).

[0013] The term “LDPE” may also be referred to as “high-pressure ethylene polymer” or “highly branched polyethylene” and is defined to mean that the polymer is partly or entirelyhomopolymerized or copolymerized in autoclave or tubular reactors at pressures above14,500 psi (100 MPa) with the use of free-radical initiators, such as peroxides (see, for example, U.S. Patent No. 4,599,392, which is hereby incorporated by reference in itsentirety). LDPE resins typically have a density in the range of 0.916 g / cm 3 to 0.930 g / cm3.

[0014] The term “LLDPE,” includes resin made using Ziegler-Natta catalyst systems as well as resin made using single-site catalysts, including, but not limited to, bis-metallocene catalysts (sometimes referred to as “m-LLDPE”), phosphinimine, and constrained geometry catalysts, and resins made using post-metallocene, molecular catalysts, including, but not limited to, bis(biphenylphenoxy) catalysts (also referred to as polyvalent aryloxyether catalysts). LLDPE includes linear, substantially linear, or heterogeneous ethylene-based copolymers. LLDPEs contain less long chain branching than LDPEs and include the substantially linear ethylene polymers, which are further defined in U.S. Patent No. 5,272,236, U.S. Patent No. 5,278,272, U.S. Patent No. 5,582,923 and U.S. Patent No. 5,733,155 each of which are incorporated herein by reference in their entirety; the homogeneously branched linear ethylene polymer compositions such as those in U.S. Patent No. 3,645,992 which is incorporated herein by reference in its entirety; the heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Patent No. 4,076,698 which is incorporated herein by reference in its entirety; and blends thereof such as those disclosed in U.S. Patent No. 3,914,342 and U.S. Patent No. 5,854,045 which are incorporated herein by reference in their entirety. The LLDPE resins can be made via gas-phase, solution-phase, or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art.86020-WO-PCT / DOW 86020 WO

[0015] The term “HDPE” generally refers to polyethylenes having densities greater than about 0.940 g / cm3and up to about 0.970 g / cm3, which are generally prepared with Ziegler- Natta catalysts, chrome catalysts or single-site catalysts including, but not limited to, substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocene), constrained geometry catalysts, phosphinimine catalysts & polyvalent aryloxyether catalysts (typically referred to as bisphenyl phenoxy).

[0016] The term “independently selected” followed by multiple options is used herein toindicate that the individual R groups appearing before the term, such as R 1, R2, R3, R4, R5,and RCcan be identical or different, without dependency on the identity of any other group also appearing before the term (e.g., R1, R2, R3, R4, and R5may all be substituted alkyls or R1and R2may be a substituted alkyl and R3may be an aryl, etc.). Use of the singular includes use of the plural and vice versa (e.g., a hexane solvent, includes hexanes). A named R group will generally have the structure that is recognized in the art as corresponding to R groups having that name. These definitions are intended to supplement and illustrate, not preclude, the definitions known to those of skill in the art.

[0017] When used to describe certain carbon atom-containing chemical groups, a parenthetical expression having the form “(Cx−Cy)” means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, a (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 the chemical group is determined by adding to both x and y the combined sum of the number of carbon atoms from all of the carbon atom-containing substituents RS.

[0018] The term “substitution” means that at least one hydrogen atom (−H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., RS). The term “persubstitution” means that every hydrogen86020-WO-PCT / DOW 86020 WO 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” areinterchangeable, and unless clearly specified have identical meanings.

[0019] 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. Examples of (C1−C30)hydrocarbyl are unsubstituted or substituted (C1−C30)alkyl, (C3−C30)cycloalkyl, (C3−C20)cycloalkyl-(C1−C10)alkylene, (C6−C30)aryl, or (C6−C20)aryl-(C1-C10)alkylene (such as benzyl (−CH2−C6H5)). Examples of (C1−C50)hydrocarbyl are unsubstituted or substituted (C1−C50)alkyl, (C3−C50)cycloalkyl, (C3−C20)cycloalkyl-(C1−C20)alkylene, (C6−C40)aryl, or (C6−C20)aryl-(C1-C20)alkylene (such as benzyl (−CH2−C6H5)).

[0020] The term “(C1−C50)alkyl” means a saturated straight or branched hydrocarbonradical of from 1 to 50 carbon atoms that is unsubstituted or substituted by one or more R S.Other alkyl groups (e.g., (Cx−Cy)alkyl) are defined in an analogous manner as having from xto y carbon atoms and being either unsubstituted or substituted with one or more R S.Examples of unsubstituted (C1−C50)alkyl are unsubstituted (C1−C20)alkyl; unsubstituted (C1−C10)alkyl; unsubstituted (C1−C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2- butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Examples of substituted (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.86020-WO-PCT / DOW 86020 WO

[0021] The term “(C6−C40)aryl” means an unsubstituted or substituted (by one or more RS) mono-, bi- or tricyclic aromatic hydrocarbon radical of from 6 to 40 carbon atoms, of which at least from 6 to 14 of the carbon atoms are aromatic ring carbon atoms. Other aryl groups (e.g., (Cx−Cy)aryl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more RS. A monocyclic aromatic hydrocarbon radical includes one aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or non- fused and aromatic or non-aromatic. Examples of unsubstituted (C6−C40)aryl include: unsubstituted (C6−C20)aryl, unsubstituted (C6−C18)aryl; 2-(C1−C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl;naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (C 6−C40)arylinclude: substituted (C1−C20)aryl; substituted (C6−C18)aryl; 2,4-bis([C20]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-l-yl.

[0022] 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.

[0023] 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-86020-WO-PCT / DOW 86020 WO 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.

[0024] The term “(C1−C50)alkylene” means a saturated straight chain or branched chaindiradical (i.e., the radicals are not on ring atoms) of from 1 to 50 carbon atoms that isunsubstituted or substituted by one or more RS. Other alkylenee groups (e.g., (Cx−Cy)alkylene) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more RS. Examples of unsubstituted (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.

[0025] 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.

[0026] The term “heteroatom” refers to an atom other than hydrogen or carbon. Examples of groups containing one or more than one heteroatom include O, S, S(O), S(O)2, Si(RC)2, P(RP), N(RN), −N=C(RC)2, −Ge(RC)2−, or −Si(RC)−, where each RCand each RPis unsubstituted (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 a86020-WO-PCT / DOW 86020 WO 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 singleheteroatom. Additionally, one of the two radicals of the diradical may be on a carbon atomand 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.

[0027] 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.

[0028] The (C1−C30)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (C1−C30)heterohydrocarbyl include (C1−C30)heteroalkyl, (C1−C30)hydrocarbyl-O−, (C1−C30)hydrocarbyl-S−, (C1−C30)hydrocarbyl-S(O)−, (C1−C30)hydrocarbyl-S(O)2−, (C1−C30)hydrocarbyl-Si(RC)2−, (Cl−C30)hydrocarbyl-N(RN)−, (Cl−C30)hydrocarbyl-P(RP)−, (C2−C30)heterocycloalkyl, (C2−C20)heterocycloalkyl- (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.86020-WO-PCT / DOW 86020 WO

[0029] The term “(C3−C50)heteroaryl” means an unsubstituted or substituted (by one or more RS) mono-, bi-, or tricyclic heteroaromatic hydrocarbon radical of from 3 to 50 total carbon atoms and from 1 to 10 heteroatoms. A monocyclic heteroaromatic hydrocarbon radical includes one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical has two rings; and a tricyclic heteroaromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring or rings of the heteroaromatic radical may be independently fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., (Cx−Cy)heteroaryl generally, such as (C4−C12)heteroaryl) are defined in an analogous manner as having from x to y carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or substituted by one or more than one RS. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered ring or a 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1, 2, or 3; and each heteroatom may be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1- yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1 or 2 and the heteroatoms may be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon radicals include pyridine-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical can be a fused 5,6- or 6,6-ring system. Examples of the fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radical are indol- 1-yl; and benzimidazole-1-yl. Examples of the fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical can be a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6-ring system. An Example of the fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An Example of the fused 5,6,6-ring system is 1H-benzo[f] indol-1-yl. An Example of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An Example of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An Example of the fused 6,6,6-ring system is acrydin-9-yl.

[0030] 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 branched86020-WO-PCT / DOW 86020 WO 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.

[0031] 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.

[0032] 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−).

[0033] 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 ormore 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. Polymerization Methods

[0034] According to embodiments disclosed herein, a method of making polyethylene may comprise polymerizing, in a slurry phase reactor, ethylene monomer and optionally at least one C3 to C20 1-alkene comonomer and a catalyst system, in an inert hydrocarbon liquid thereby forming a polyethylene.

[0035] In embodiments, the polymerization may occur in a slurry-phase polymerization reactor, such as a well-stirred reactor. In embodiments, the slurry phase polymerization process occurs in one or more loop reactors or one or more spherical isothermal reactors. A86020-WO-PCT / DOW 86020 WO catalyst system may be suspended in an inert hydrocarbon liquid and then contacted with an inert hydrocarbon liquid comprising the ethylene monomer and optionally the at least one C3to C201-alkene comonomer. Ethylene, one or more solvents, one or more catalyst systems, such as the catalyst system described herein, and optionally one or more comonomers are fed continuously to the one or more reactors. Exemplary solvents for use as the inert hydrocarbon liquid include, but are not limited to, isobutane, isopentane, pentane, hexane, hexanes, heptane, octane, petroleum ether, methylcyclohexane, and isoparaffins. For example, such solvents are commercially available under the name ISOPAR E from ExxonMobil Chemical Co., Houston, Texas.

[0036] In embodiments, the concentration of supported catalyst in the slurry reactor may be up to 50 wt. % solid supported catalyst suspended in the inert hydrocarbon liquid. In embodiments, the concentration of supported catalyst in the slurry reactor may up to 40 wt. %, up to 30 wt. %, up to 20 wt. %, up to 10 wt. %, up to 5 %, up to 1 %, from 0 to 0.001 wt. %, from 0.001 to 0.01 wt. %, from 0.01 to 0.1 wt. %, from 0.1 to 50 wt. %, from 0.1 to 1 wt. %, from 1 wt. % to 5 wt. %, from 5 wt. % to 10 wt. %, from 10 wt. % to 20 wt. %, from 20 wt. % to 30 wt. %, from 30 wt. % to 40 wt. %, from 40 wt. % to 50 wt. %, or any combination of two or more of these ranges of solid supported catalyst suspended in the inert hydrocarbon liquid.

[0037] In embodiments, the slurry phase polymerization occurs in the reactor at a temperature of less than or equal to 130 °C. For example, the reactor temperature of the slurry-phase polymerization reactor may be from 75 ºC to 115 ºC, from 30 °C to 45 °C, from 45 °C to 60 °C, from 60 °C to 70 °C, from 70 °C to 75 °C, from 75 °C to 80 °C, from 80 °C to 85 °C, from 85 °C to 90 °C, from 90 °C to 95 °C, from 95 °C to 100 °C, from 100 °C to 105 °C, from 105 °C to 110 °C, from 110 °C to 115 °C, from 115 °C to 130 °C, or any combination of two or more of these ranges.

[0038] In embodiments, gasses may be used to pressurize the slurry-phase reactor to a pressure of from 690 kPa (100 psig) to 6,896 kPa (1,000 psig). For example, the reactor pressure of the slurry-phase polymerization reactor may be from 690 kPa (100 psig) to 1,379 kPa (200 psig), from 1,379 kPa (200 psig) to 2068 kPa (300 psig), from 2068 kPa (300 psig) to 2,759 kPa (400 psig), from 2,759 kPa (400 psig) to 3,448 kPa (500 psig), or any combination of two or more of these ranges.86020-WO-PCT / DOW 86020 WO

[0039] In embodiments, ethylene may be one of the gasses used to pressurize the slurry- phase polymerization reactor. In embodiments, the ethylene partial pressure may be up to 2413 kPa (350 psig), such as from 35 kpa (5 psig) to 137 kPa (20 psig), from 137 kPa (20 psig) to 345 kPa (50 psig), from 345 kPa (50 psig) to 689 kPa (100 psig), from 689 kPa (100 psig) to 1034 kPa (150 psig), from 1034 kPa (150 psig) to 1378 kPa (200 psig), from 1378 kPa (200 psig) to 1723 kPa (250 psig), from 1723 kPa (250 psig) to 2068 kPa (300 psig), from 2068 kPa (300 psig) to 2413 kPa (350 psig), or any combination of two or more of these ranges.

[0040] In embodiments, hydrogen may be added during polymerization to control the final properties of the polyethylene. The amount of hydrogen used during polymerization may be expressed as a mole ratio relative to the total polymerizable monomer, such as, for example, ethylene. The amount of hydrogen used in the polymerization process may be an amount necessary to achieve the desired properties of the polyethylene, such as, for example, melt flow rate. In embodiments, the mole ratio of hydrogen to total polymerizable monomer (e.g., H2:monomer, also referred to herein as “H2:C2,” H2 / C2, or “H2 / C2”) is greater than 0.0001. For example, the mole ratio of hydrogen to total polymerizable monomer (H2:C2) may be from 0.0001 to 1.8, from 0.0001 to 1.0, from 0 to 0.1, from 0.0001 to 0.10, from 0.0001 to 0.001, from 0.0001 to 0.0005, from 0.0005 to 1.8, from 0.0005 to 1.0, from 0.0005 to 0.10, from 0.0005 to 0.001, from 0.001 to 1.8, from 0.001 to 1.0, from 0.001 to 0.10, from 0.001 to 0.05, or from 0.001 to 0.005, or any combination of two or more of these ranges. It should be understood that “total polymerizable monomer” refers to the amount of ethylene in thereactor which has not yet been covalently bonded to another compound.

[0041] In some embodiments where the at least one C3 to C201-alkene comonomer is used during polymerization, the ratio between the at least one C3 to C201-alkene comonomer to the ethylene monomer (also referred to herein as a comonomer-to-ethylene ratio) in the polymerization reactor may be from 0 to 2.0 , such as from 0 to 0.0001, from 0.0001 to 0.001, from 0.001 to 0.01, from 0.01 to 0.1, from 0.1 to 1.0, from 1.0 to 2.0, or any combination of two or more of these ranges.

[0042] In one or more embodiments, the polymerization process produces greater than or equal to 300 grams of the polyethylene per grams of the spray-dried catalyst system per hour (gpoly / gcat·hour). In some embodiments, the process produces at to 400 gpoly / gcat·hour, at least86020-WO-PCT / DOW 86020 WO 450 gpoly / gcat·hour, at least 500 gpoly / gcat·hour, at least 600 gpoly / gcat·hour, at least 700 gpoly / gcat·hour, at least 800 gpoly / gcat·hour, at least 900 gpoly / gcat·hour, at least 1000 gpoly / gcat·hour, at least 1200 gpoly / gcat·hour, at least 1500 gpoly / gcat·hour, at least 2000 gpoly / gcat·hour, at least 5,000 gpoly / gcat·hour, or at least 75,000 gpoly / gcat·hour. Reaction Constituents

[0043] As mentioned above, the method of making polyethylene may comprise polymerizing, in a slurry phase polymerization reactor, ethylene monomer and optionally at least one C3to C201-alkene comonomer and a catalyst system. The optional at least one C3to C81-alkene comonomer, may comprise any C3to C201-alkene comonomer, such as a 1- propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, or 1-octene.

[0044] The catalyst system may comprise at least a procatalyst. 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 manne r thatconverts the procatalyst to a catalytically active catalyst. As used herein, the terms “activatingco-catalyst” and “activator” are interchangeable terms.

[0045] The procatalyst may have a structure according to Formula (I):

[0046] M is a metal. In some embodiments, M is chosen from titanium, zirconium, or hafnium. In some embodiments, M is zirconium or hafnium. Metal M may have a formal oxidation state of +2 or +3.

[0047] 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 a86020-WO-PCT / DOW 86020 WO (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, and (C3-C30)heteroaryl. n is 1 or 2. Q is a monoanionic spectator ligand selected from (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C5-C30)aryl, and (C3-C30)heteroaryl, wherein Q is different from each X; 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. Each RCis independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3- C30)heteroaryl, and –H. In some embodiments, each X is independently selected from (C1−C10)alkyl, (C6−C20)aryl, or a halogen; and each R1 is a (C1−C30)alkyl, or a (C6−C30)aryl. Formula (I) is overall charge neutral.

[0048] In one or more embodiments, in Formula (I), R1is (C6−C30)aryl.

[0049] 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.

[0050] In one or more embodiments, R1 is (C1−C12)alkyl, (C1−C12)cycloalkyl, trimethylsilyl methyl, benzyl, or 1-adamantyl.

[0051] In one or more embodiments, the (C1−C30)hydrocarbyl of R2and R3may be a (C6−C30)aryl and the (C1−C30)heterohydrocarbyl of R2 and R3 may be a (C3−C30)heteroaryl.

[0052] In one or more embodiments, each X is independently selected from methyl, benzyl, phenyl, trimethylsilyl methyl, or chloro.

[0053] In some optional embodiments, R2 and R3 are covalently linked to form a ring. Insuch embodiments, the procatalyst has a structure according to Formula (II):86020-WO-PCT / DOW 86020 WO

[0054] In Formula (II), each R1, Q, X, n, and M are defined as in Formula (I); and each R4, R5, R6, and R7are independently (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, (C6- C40)aryl, (C3-C40)heteroaryl, a halogen, or –H.

[0055] In various embodiments, R4 is (C6−C40)aryl or (C3−C40)heteroaryl.

[0056] 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.

[0057] In various embodiments, R5, R6, and R7 are –H.

[0058] 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.

[0059] In one or more embodiments, Q is a monoanionic spectator ligand selected from (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C5–C30)aryl, and (C3–C30)heteroaryl, wherein Q is different from each X. In particular embodiments, Q may be unsubstituted or substituted cyclopentadienyl. Without intent to be bound by theory, it is believed that the heteroleptic nature of the 2-amino-thiazole complexes described herein, i.e., wherein Q isdifferent from each X, may be advantageous for achieving improved catalyst activity andtunable polymer properties, relative to homoleptic 2-amino-thiazole complexes wherein the ligands bonded to the metal center, other than the 2-amino-thiazole ligand, are the same (e.g., three benzyl ligands). Further, it has been unexpectedly found that embodiments of the heteroleptic 2-amino-thiazole complexes described herein have increased catalyst activities relative to their homoleptic analogs, or produce polymers with low comonomer incorporation86020-WO-PCT / DOW 86020 WO -18- and variable weight-average molecular weight, the combination of which is believed to befavorable for polymer processability, or a combination of both.

[0060] In some embodiments, Q is chosen from formulas (III), (IV), (V), or (VI); where the wavy line indicates a point of attachment to the M of Formula (I):86020-WO-PCT / DOW 86020 WO

[0061] R8, R9, and R10may be independently chosen from (C1−C30)hydrocarbyl, (C1- C30)heterohydrocarbyl, (C6–C30)aryl, and (C3–C30)heteroaryl. R11R12, R13, and R14, may be independently chosen from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, −Si(RC)3, −Ge(RC)3, −N(RN)2, −ORC, and –H. Each RNand RCmay be independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, and –H. Optionally, R11 and R12, or R11 and R13, or R11 and R14, or R13 and R14, or R12 and R13, or R12 and R14may be covalently connected to form an aromatic ring or non-aromatic ring. Each of R15-R26 may be independently chosen from –H, (C1-C30)hydrocarbyl, (C1- C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, −Si(RC)3, or −Ge(RC)3. Optionally R15and R16, R16and R17, R17and R18, R18and R19, R20and R21, R21and R22, R22and R23, R24and R25, or R25and R26are covalently linked to form one or more ring or multi-ring structures.. In embodiments, R15-R26 are independently chosen from –H and (C1-C10)alkyl.

[0062] Specific embodiments of procatalysts are disclosed as formulas (IIa) through (IIl):Formula (IIa) Formula (IIb)86020-WO-PCT / DOW 86020 WOFormula (IIe) Formula (IIf)Formula (IIg) Formula (IIh)86020-WO-PCT / DOW 86020 WOFormula (IIk) Formula (IIl) Supported Catalyst Systems

[0063] In some embodiments, the catalyst system is a supported catalyst system comprising: the procatalyst; an activator; and a support.

[0064] As mentioned above, the procatalyst may be rendered catalytically active by contacting it to, or combining it with, an activator. The term “activator” may include any combination of reagents that increases the rate at which a procatalyst oligomerizes or polymerizes unsaturated monomers, such as olefins. An activator may also affect the86020-WO-PCT / DOW 86020 WO molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer produced. The procatalyst may be activated for oligomerization and / or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and or polymerization. In some embodiments, the activator is a supportedactivator, that is, the activator is supported on a support material.

[0065] Alumoxane activators may be utilized as an activator for one or more of the procatalysts described herein. Alumoxane(s) or aluminoxane(s) are generally oligomeric compounds containing –Al(R)–O– subunits, where R is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide. Mixtures of different alumoxanes and modified alumoxanes may also be used. For further descriptions, see U.S. Patent Nos. 4,665,208; 4,952,540; 5,041,584; 5,091,352; 5,206,199; 5,204,419; 4,874,734; 4,924,018; 4,908,463; 4,968,827; 5,329,032; 5,248,801; 5,235,081; 5,157,137; 5,103,031; and EP 0561476; EP 0279586; EP 0516476; EP 0594218; and WO 94 / 10180. In embodiments, the activator comprises methylalumoxane (MAO), such as solid methylalumoxane (SMAO).

[0066] Aluminum alkyl or organoaluminum compounds that may be utilized as activators(or scavengers) including trimethylaluminum, triethylaluminum, triisobutylaluminum, tri -n-hexylaluminum, tri-n-octylaluminum and the like.

[0067] In embodiments, the molar ratio of metal in the activator to metal in the procatalystis from 0.5:1 to 3500:1, such as from 0.5:1 to 1:1, from 1:1 to 5:1, from 5:1 to 10:1, from 10:l to 20:1, from 20:1 to 50:1, from 50:1 to 100:1, from 100:1 to 250:1, from 250:1 to 500:1, from 500:1 to 1000:1, from 1000:1 to 1500:1, from 1500:1 to 2000:1, from 2000:1 to 2500:1, from 2500:1 to 3000:1, from 3000:1 to 3500:1, or any combination of two or more of these ranges.

[0068] In embodiments, the procatalyst can be utilized to make supported catalyst systems or compositions. In some embodiments the procatalyst and support material are contacted together in an inert hydrocarbon liquid to give a suspension in the inert hydrocarbon liquid, then the suspension is contacted with the activator to give a suspension of the supported86020-WO-PCT / DOW 86020 WO catalyst system in the inert hydrocarbon liquid, and then inert hydrocarbon liquid is removed to give the supported catalyst system.

[0069] In embodiments, the procatalyst, the activator, or both, may be disposed on one or more support materials. For example, the procatalyst 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 procatalyst, the activator, 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 procatalyst, the activator, 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.

[0070] In some embodiments the activator and the support material are contacted together in an inert hydrocarbon liquid to give a suspension of a supported activator 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 inerthydrocarbon liquid is removed to give the supported catalyst system.

[0071] 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 inorganicchlorides. Other support materials include resinous support materials, e.g., polys tyrene,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.

[0072] 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 include dehydrated silica, 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.86020-WO-PCT / DOW 86020 WO Patent No.5,965,477), montmorillonite (e.g., as described in European Patent No.0511665), phyllosilicate, zeolites, talc, clays (e.g., as described in U.S. Patent No. 6,034,187), and mixtures of these. In other embodiments, combinations of these support materials may be used, such as, for example, silica-chromium, silica-alumina, silica-titania, and combinations of these. Additional support materials may also include those porous acrylic polymers described in European Patent No. 0 767 184. 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.

[0073] 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.

[0074] 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.86020-WO-PCT / DOW 86020 WO

[0075] The support material may be uncalcined or calcined. The calcined support material is made prior to being contacted with a procatalyst, activator, 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.

[0076] In embodiments, the supported catalyst system may be produced by spray drying. For example, at least one of the procatalyst, the activator, and the support may be spray dried. As used herein, a “spray-dried” material refers to a material comprising components that have undergone a spray-drying process. Various spray-drying processes are known in the art and are suitable for forming the spray-dried catalyst systems disclosed herein.

[0077] In some embodiments, a mixture of procatalyst, support, activator, and inert hydrocarbon liquid may be formed. The mixture may then be spray dried to form a spray- dried supported catalyst system. Spray‑drying the mixture removes the inert hydrocarbon solvent to produce spray‑dried particles, though spray‑drying the mixture may not result in complete removal of liquids from the resulting catalyst system. That is, the spray‑dried catalyst system may include residual amounts (i.e., from 1 wt. % to 3 wt. %) of the inert hydrocarbon solvent. A number of other known components may be utilized in the spray- drying process. An atomizer, such as an atomizing nozzle or a centrifugal high speed disc, for example, may be used to create a spray or dispersion of droplets of the composition. The droplets of the composition may then be rapidly dried by contact with an inert drying gas. The inert drying gas may be any gas that is non-reactive under the conditions employed during atomization, such as nitrogen, for example. The inert drying gas may meet the composition at the atomizer, which produces a droplet stream on a continuous basis. Dried particles of the composition may be trapped out of the process in a separator, such as a cyclone, for example, which can separate solids formed from a gaseous mixture of the drying gas, solvent, and other volatile components. Generally, it is believed that spray drying may improve the productivity, efficiency, and / or resulting polymer properties of at least some of the catalyst systems described herein.86020-WO-PCT / DOW 86020 WO

[0078] In some embodiments, methods for producing the spray‑dried catalyst system include spray‑drying a mixture comprising an inert hydrocarbon liquid, a support material, and an activator, thereby forming a spray‑dried supported activator, and then contacting the spray‑dried supported activator with an inert hydrocarbon liquid and the procatalyst to make the spray-dried supported catalyst system. Further embodiments include preparing a trim solution comprising the second inert hydrocarbon liquid and the procatalyst and then contacting the trim solution with the spray‑dried supported activator. In embodiments where a spray‑dried supported activator is contacted with an inert hydrocarbon liquid and theprocatalyst, the resulting mixture may be added directly, i.e., without an additional dryingstep, to a polymerization reactor (e.g., a slurry-phase polymerization reactor), or may be conventionally‑dried or spray‑dried to produce a dried supported catalyst system which is added to a polymerization reactor, or the dried supported catalyst system may be resuspendedin an inert hydrocarbon liquid, and the resulting slurry is added to a polymerization reactor.

[0079] In some embodiments, a mixture of the procatalyst, the support, and the activator in an inert hydrocarbon liquid are used without drying. For example, the supported catalyst system in the inert hydrocarbon liquid may be made in-line prior to entry or injection into the slurry-phase polymerization reactor and is utilized for a polymerization reaction in the reactor directly without a drying or decanting step. In some embodiments, contacting a mixture of the procatalyst and an inert hydrocarbon liquid with a supported or spray dried activator particle is performed in-line to a polymerization reactor.

[0080] The spray-dried catalyst systems disclosed herein may have the form of a free- flowing powder, for instance. After the spray-drying process, the spray-dried catalyst system and a number of known components may be utilized to form a slurry. The spray-dried catalyst system may be utilized with a diluent to form a slurry suitable for use in olefin polymerization, for example. In one or more embodiments, the slurry may be combined with one or more additional catalysts or other known components prior to delivery into a polymerization reactor.

[0081] In some embodiments, a mixture of the procatalyst, the support, and the activator in an inert hydrocarbon liquid are spray-dried to form a spray-dried catalyst system, and the supported catalyst system is contacted with the procatalyst in an inert hydrocarbon liquid,86020-WO-PCT / DOW 86020 WO prior to entry or injection into the slurry-phase polymerization reactor, and is utilized for apolymerization reactor in the reactor directly without a drying or decanting step.

[0082] In some embodiments, the procatalyst in an inert hydrocarbon liquid is mixed with a supported activator to form the supported catalyst system in an inert hydrocarbon liquid, which is then injected into the slurry-phase polymerization reactor, and is utilized in thepolymerization reactor directly without a drying or decanting step.

[0083] In some embodiments, the procatalyst in an inert hydrocarbon liquid is mixed with a supported activator to form the supported catalyst system in an inert hydrocarbon liquid, further diluted with a second inert hydrocarbon liquid, and then injected into the slurry-phase polymerization reactor, and is utilized in the polymerization reactor directly without a drying or decanting step.

[0084] In some embodiments, the procatalyst in an inert hydrocarbon liquid is mixed with a supported activator to form the supported catalyst system in an inert hydrocarbon liquid, which is then dried, or the liquid is decanted. The resulting supported catalyst system is then further diluted with a second inert hydrocarbon liquid, and is the slurry of the supported catalyst system is then injected into the slurry-phase polymerization reactor.

[0085] The inert hydrocarbon liquid may comprise a mineral oil, a hydrocarbon solvent, or a combination thereof. The second inert hydrocarbon liquid may have the same or a different composition from the first inert hydrocarbon liquid. Polyethylenes

[0086] In embodiments, the supported catalyst system of the present disclosure may be utilized to polymerize a single type of olefin, producing a homopolymer. However, additional 1-alkenes (also called alpha-olefins) may be incorporated into the polymerization scheme in other embodiments. The additional 1-alkene comonomers typically have no more than 20 carbon atoms. For example, the supported catalyst systems of the present disclosure may be utilized to polymerize ethylene monomer and at least one 1-alkene comonomer. Exemplary 1-alkene comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1- hexene, 1-heptene, 1-octene and 4-methyl-l-pentene. For example, the at least one 1-alkene comonomer may be selected from the group consisting of propylene, 1-butene, 1-hexene, and86020-WO-PCT / DOW 86020 WO 1-octene; or, in the alternative, from the group consisting of 1-hexene and 1-octene. In embodiments, the at least one 1-alkene comonomer comprises 1-butene or 1-hexene.

[0087] As mentioned above, the method produces a polyethylene. In some embodiments, from 95 – 99.99 wt. %, such as from 95 to 96 wt. %, from 96 to 97 wt. %, from 97 to 98 wt. %, from 98 to 99 wt. %, from 99 to 99.5 wt. %, from 99.5 to 99.9 wt. %, or any combination of two or more of these ranges of units of the polyethylene comprise ethylene based on a total weight of the polyethylene, and 0.01-5 wt. %, such as from 0.01 to 0.05 wt. %, from 0.05 to 0.1 wt. %, from 0.1 wt. % to 0.5 wt. %, from 0.5 wt. % to 1 wt. %, from 1 wt. % to 2 wt. %, from 2 wt. % to 3 wt. %, from 3 wt. % to 4 wt. %, from 4 wt. % to 5 wt. %, or any combinationof two or more of these ranges of units of the polyethylene comprise the at least one C 3 to C81-alkene comonomer, based on the total weight of the polyethylene.

[0088] In some embodiments, the polyethylene may have a melt temperature from 125 °C to 140 °C, such as from 125 °C to 130 °C, from 130 °C to 135 °C, from 135 °C to 140 °C, or any combination of two or more of these ranges.

[0089] The polyethylenes 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 polyethylenes may compromise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the polyethylenes and the one or more additives. The polyethylenes may further comprise fillers, which may include, but are not limited to, organic or inorganic fillers. The polyethylenes 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 polyethylenes and all additives or fillers. The polyethylenes mayfurther be blended with one or more polymers to form a blend.

[0090] The produced polyethylene may be used in a wide variety of products and end-use applications. The produced polyethylene may also be blended and / or co-extruded with any other polymer. Non-limiting examples of other polymers include linear low-density polyethylene, elastomers, plastomers, high pressure low density polyethylene, high density polyethylene, polypropylenes, and the like. The produced polyethylene and blends including86020-WO-PCT / DOW 86020 WO the produced polyethylene may be used to produce blow-molded components or products, among various other end uses. The produced polyethylene and blends including the produced polyethylene may be useful in forming operations such as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding. Films may include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, and membranes in food-contact and non-food contact applications. Fibers may include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, and geotextiles. Extruded articles may include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners. Molded articles may include single and multi-layered constructions in the form of bottles,tanks, large hollow articles, rigid food containers and toys.

[0091] Some embodiments of the methods described in this disclosure yield unique polymer properties (e.g., broad melt flow ratios of the polymers formed) and the amount of the comonomers incorporated into the polymers.

[0092] One or more features of the present disclosure are illustrated in view of the examples as follows: TEST METHODS Differential Scanning Calorimetry (DSC):

[0093] Melt temperature was determined via Differential Scanning Calorimetry according to ASTM D 3418-08. In general, a scan rate of 10° C / min on a sample of 10 mg was used, and the second heating cycle was used to determine Tm. Conventional Gel Permeation Chromatography (GPC)

[0094] Molecular weights (e.g., Mp, Mw, Mz, and Mn) are determined by GPC. 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 (10µL) was added to each sample for use as an internal flow marker. Samples were first diluted in 1,2,4-trichlorobenzene (TCB) stabilized with 300ppm86020-WO-PCT / DOW 86020 WO butylated hydroxyl toluene (BHT) at a concentration of 10mg / 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 7.5mm) guard column followed by two PL-gel 20 µm (300 x 7.5mm) 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 (MW) Agilent EasiCal polystyrene standards (PS-1 and PS-2) were analyzed to create a 3rd order MW calibration curve. Molecular weight units were converted from polystyrene (PS) to polyethylene (PE) using a daily Q-factor calculated around 0.4 using the average of 5 Dow 38-4 reference samples of known MW. Comonomer incorporation was determined by use of a linear calibration developed by analyzing ethylene-octene samples with known compositions. ASPECTS

[0095] 1. A method of making polyethylene comprising: polymerizing in a slurry phase reactor ethylene monomer and optionally at least one C3to C201-alkene comonomer in the presence of a suspension comprising a supported catalyst system in an inert hydrocarbonliquid, the supported catalyst system comprising an activated complex of formula (I):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 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; n86020-WO-PCT / DOW 86020 WO is 1 or 2; Q is a monoanionic spectator ligand selected from (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C5-C30)aryl, and (C3-C30)heteroaryl, wherein Q is different from X; 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, wherein each RCis independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3- C30)heteroaryl, and –H.

[0096] 2. The method of any preceding aspect, wherein: each X is independently selected from (C1−C10)alkyl, (C6−C20)aryl, or a halogen; and each R1 is independently a (C1−C30)alkyl, or a (C6−C30)aryl.

[0097] 3. The method of any preceding aspect, wherein R2and R3are covalently linked to form an aromatic ring, and the metal−ligand complex has a structure according to formula (II):where each R4, R5, R6, and R7are independently (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, (C6-C40)aryl, (C3-C40)heteroaryl, a halogen, or –H.

[0098] 4. The method of any preceding aspect wherein R1 is (C6−C30)aryl; R4 is phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, or a carbozolyl; and R5, R6, and R7, are −H.86020-WO-PCT / DOW 86020 WO

[0099] 5. The method of any preceding aspect, wherein Q is chosen from formulas:wherein: R8, R9, and R10are independently chosen from (C1−C30)hydrocarbyl, (C1- C30)heterohydrocarbyl, (C6–C30)aryl, and (C3–C30)heteroaryl; R11 R12, R13, and R14, are independently chosen from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, −Si(RC)3, −N(RN)2, −ORC, and –H, wherein each RNand RCis independently selected from the group consisting of86020-WO-PCT / DOW 86020 WO (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, and –H, and optionally R11and R12, or R11and R13, or R11and R14, R13and R14, or R12and R13, or R12and R14 may be covalently connected to form an aromatic ring or non-aromatic ring; and R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 R25, and R26 are independently chosen from –H, (C1- C30)hydrocarbyl, (C1-C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, −Si(RC)3, or -Ge(RC)3; and optionally R15 and R16, R16 and R17, R17 and R18, R18 and R19, R20 and R21, R21 and R22, R22 and R23, R24 and R25, or R25 and R26 are covalently linked to form one or more ring or multi-ring structures.6. The method of any preceding aspect, wherein Q is Formula (V) or Formula (VI).

[0100] 7. The method of aspect 6, wherein R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 R25, and R26 are independently chosen from –H and (C1-C12)hydrocarbyl.

[0101] 8. The method of any one of aspects 1-7, wherein R1is a phenyl, 2,6- dimethylphenyl, 1-naphthyl, 2-naphthyl, or adamantyl.

[0102] 9. The method of any one of the aspects 3-8, wherein R4 is a phenyl, 2,6- dimethylphenyl, or 2,4,6-trimethylphenyl.

[0103] 10. The method of any one of aspects 1-9, wherein the structure (II) is representedby anyone of the structures (IIa) through (IIl):; ;86020-WO-PCT / DOW 86020 WOstructure (IIl);86020-WO-PCT / DOW 86020 WO

[0104] 11. The method according to aspects 1-10, wherein the catalyst system is a supported catalyst system comprising: the structure represented by Formula (I) or Formula (II); an activator; and a support.

[0105] 12. The method of aspect 11, wherein the support comprises silica or fumed silica.

[0106] 13. The method of any one of aspects 11-12, wherein the activator comprises methylaluminoxane.

[0107] 14. The method of any one of aspects 11-13, wherein the molar ratio of metal in the activator to Group IV metal in the structure represented by Formula I or Formula II is from 3,500 : 1 to 0.5 : 1.

[0108] 15. The method of any one of aspects 11-14, wherein the activator is a supported activator.

[0109] 16. A method of making the supported catalyst system of any one of aspects 11-14 comprising step (a), comprising steps (b) and (c), comprising step (d), or comprising steps (e) and (f): (a) spray drying a mixture of an inert hydrocarbon liquid, the structure represented by Formula (I) or Formula (II), the support material, and the activator to make the spray- dried supported catalyst system; or (b) spray drying a mixture of an inert hydrocarbon liquid, the support material and the activator to make a spray-dried supported activator, and (c) mixing the structure represented by Formula (I) or Formula (II) with the spray-dried supported activator and an inert hydrocarbon liquid to make the supported catalyst system; or (d) drying a mixture of an inert hydrocarbon liquid, the structure represented by Formula (I) or Formula (II), the support material, and the activator to make the supported catalyst system; or (e) drying a mixture of an inert hydrocarbon liquid, the support and activator to make a supported activator, and (f) mixing the structure represented by Formula (I) or Formula (II) with the supported activator and an inert hydrocarbon liquid to make the supported catalyst system.

[0110] 17. The method of any one of aspects 11-14 , wherein: a) the activator is added to the support in the inert hydrocarbon liquid, and then the complex represented by Formula I or Formula II is added to make an activated supported catalyst system; or b) the support is added to the activator in the inert hydrocarbon liquid, and then the procatalyst represented by86020-WO-PCT / DOW 86020 WO Formula I or Formula II is added to make an activated supported catalyst system; or c) the complex represented by Formula I or Formula II is added to the activator in a hydrocarbon liquid, and then the support is added to make an activated supported catalyst system; or d) the complex represented by Formula I or Formula II is added to the support in a hydrocarbon liquid, and then the activator is added to make an activated supported catalyst system; or e) the activator is added to the support in the hydrocarbon liquid, then dried by spray drying, decanting, or application of reduced pressure, and then the complex represented by Formula I or Formula II is added to make an activated supported catalyst system; or f) the support is added to the activator in the hydrocarbon liquid, then dried by spray drying, decanting, or application of reduced pressure, and then the complex represented by Formula I or Formula II is added to make an activated supported catalyst system; or g) the complex represented by Formula I or Formula II is added to a mixture of supported activator in the inert hydrocarbon liquid to make an activated supported catalyst system; or h) the complex of Formula I or Formula II is added to a mixture of a supported activator in the inert hydrocarbon liquid, and dried to make a dried activated supported catalyst system; or i) the complex of Formula I or Formula II is added to a mixture of supported activator in the inert hydrocarbon liquid to make an activated supported catalyst system, which is then fed in line into a polymerization reactor without a drying step.

[0111] 18. The method of any one of aspects 11-14 , wherein a mixture of the complex of Formula I or Formula II, the support, and the activator in the inert hydrocarbon liquid are used without drying.

[0112] 19. The method of any one of aspects 11-14 , wherein the activator and the support are spray dried.

[0113] 20. The method of any one of aspects 11-14 and 17-19, wherein a supported catalyst system in the inert hydrocarbon liquid, is made in line prior to entry or injection into a slurry polymerization reactor and is utilized for a polymerization reaction in the reactor directly without a drying or decanting step.

[0114] 21. A method of making a catalyst system, the method comprising: contacting the complex represented by Formula I or Formula II in an inert hydrocarbon liquid with a86020-WO-PCT / DOW 86020 WOsupported or spray dried activator particle, wherein the contacting step is performed in -lineto a slurry polymerization reactor.

[0115] 22. The method of any one of aspects 11-21 , wherein the inert hydrocarbon liquidcomprises mineral oil, a hydrocarbon solvent, or a combination thereof.

[0116] 23. A method of making a polyolefin polymer, the method comprising: contacting, under polymerization conditions in a slurry polymerization reactor, an olefin with the composition of any one of the preceding aspects so as to polymerize the olefin, thereby making a polyolefin polymer.

[0117] 24. The method of aspect 23, wherein the olefin comprises ethylene, or acombination of ethylene and propylene, or a combination of ethylene and a (C 4-C20)alpha-olefin comonomer, and wherein the polyolefin polymer is an ethylene homopolymer, or an ethylene / propylene copolymer, or an ethylene (C4-C20)alpha-olefin copolymer.

[0118] 25. The method of aspect 24, wherein the (C4-C20)alpha-olefin comonomer comprises 1-butene or 1-hexene. EXAMPLES

[0119] The following examples illustrate features of the present disclosure but are not intended to limit the scope of the disclosure. The following experiments analyzed the performance of embodiments of the ethylene-based polymers described herein. Procatalysts

[0120] The structures of Procatalysts 1-12 are shown below. Procatalysts 1-12 were synthesized according to the methods described in U.S. Provisional Patent Application Nos. 63 / 665,659 and 63 / 665,661, the entirety of both of which is incorporated by reference herein.86020-WO-PCT / DOW 86020 WO86020-WO-PCT / DOW 86020 WOSupported Catalyst Preparation

[0121] In a nitrogen filled continuous purge glovebox, pre-catalysts are provided neat, in toluene, or already supported on SMAO. Unsupported pre-catalysts are diluted to 4.21 mM in anhydrous deoxygenated toluene, and pipetted into oven-dried 4 mL or 8 mL scintillation vials containing a pre-weighed amount of SMAO such that the resultant slurry is 45 µmol Ti, Zr or Hf per 1 g SMAO, unless otherwise noted. The pre-catalyst slurries are stirred at 300 rpm and heated to 50 °C for 30 minutes, then returned to ambient temperature. Colorization of the previously white SMAO indicates the catalyst has been supported, but is not quantified or recorded at this stage.1H-NMR experiments of the remaining liquid reveals no observable remaining procatalyst or active catalyst present in the liquid layer. Therefore, supporting reactions are assumed to reach full conversion. The room temperature slurries are moved to a vortexing unit and agitated at 700 rpm for uniform dispersion. Slurries are agitated for at least one minute before an aliquot may be daughtered by positive displacement tip (PDT) into an 8 mL vial, and vortexing continues during the daughtering process. Daughters (or supported catalysts) will be diluted with Isopar E to 50 – 500 nmol per mL depending on the expected parallel pressure reactor (PPR) performance. Catalyst materials and supported catalysts are kept in a glovebox freezer at -30 °C for storage. A listing of the procatalysts in each slurry is given below in Table 1. Table 186020-WO-PCT / DOW 86020 WOSlurry Reactor Testing:

[0122] 48 PPR-A reactor cells were prepared as follows the day before the PPR run. An oven-dried pre-weighed library of glass tubes were manually inserted into the reactor wells, PEEK stir paddles were attached to the module heads, and the module heads were attached to the module bodies. The reactors were heated to 150 °C, purged with nitrogen for 12 hours, and cooled to 50 °C. On the day of the experiment, the reactors were purged twice with ethylene and vented completely to purge the lines. The reactors were pre-heated to 50 °C and the set to 800 rpm.

[0123] The reactors were filled to the appropriate solvent level with Isopar-E and the comonomer (1-hexene) using the robotic needle to give a final total volume of 5 mL (once all of the reagent solutions are added later). The solvent and comonomer injections loading modules 1-3 were performed using the left robotic arm and the solvent injections loading modules 4-6 used the right robotic arm with both arms operating simultaneously. Following solvent injection, the reactors were heated to final desired temperature (100 °C) and stirring increased to programmed set points. When the reactors reached the temperature set point, which required about 10-30 minutes depending on the desired temperature, the cells were pressurized to the desired set point with either pure ethylene, or a mixture of ethylene and hydrogen from the gas accumulator, and the solvent saturated (as observed by the gas uptake). If the ethylene-hydrogen mixture was used, once the solvent was saturated in all cells, the gas feed line was switched from the accumulator to pure ethylene for the remainder of the run.

[0124] The robotic synthesis protocol was then initiated whereby the activator slurry (SMAO) was injected first, followed by the supported catalyst slurries. The reagent and chase86020-WO-PCT / DOW 86020 WO injections loading modules 1-3 were performed using the left robotic arm and the solvent injections loading modules 4-6 used the right robotic arm with both arms operating simultaneously. Both injections for a given cell were completed before the robot started the injection of the next cell in the sequence. Each reagent addition was chased with 500 µL of Isopar-E solvent to ensure the complete injection of the reagent. After each reagent addition the needles were washed with Isopar-E inside and outside the needle.

[0125] At the moment of the catalyst injection in each individual cell, a reaction timer was started and the PPR software began monitoring the pressure of each cell. The desired pressure of 103 psig for experiments run at 80 °C and 100 psig for experiments at 100 °C (within approximately 2-6 psig) was maintained by the supplemental addition of ethylene gas by opening the valve at the set point minus 2 psi and closing it when the pressure reached 2 psi above set point. All drops in pressure were cumulatively recorded as uptake of the ethylene for the duration of the run. The polymerization reactions proceeded for 90 minutes or to an ethylene uptake of 90 psi, whichever occurred first, and then were quenched by adding a 60 psi overpressure of 10% (v / v) CO2 in argon. Data collection continued for 5 minutes after the quench of each cell. After the last cell finished quenching, any potential leaks identified from the pressure and uptake curves were noted, the reactors were cooled down to 50 °C, vented, and the PPR tubes removed from the module blocks. The PPR library tubes were removed from the drybox and the volatiles then removed using the Genevac rotary evaporator. Once the library vials were re-weighed to obtain the yields, the library was submitted for high throughput polymer analytical. The individual run conditions and some polymer parameters are tabulated in Table 2 and Table 3 below. Table 286020-WO-PCT / DOW 86020 WO*Slurry PPR conditions: Temp. = 100 °C, [C2] = 0.33 M, IsoparE = 5 mL, C6 / C2 (molar ratio) = 0.6 in liquid, H2 / C2(molar ratio) = 0.0016 in liquid, run time = 90 mins max (5,400 s), Quench time = time needed to uptake 90 psi of ethylene; the faster the quench time, the more active the catalyst is. All catalysts are 45 µmol Zr or Hf / g SMAO. Table 3*Slurry PPR conditions: Temp. = 80 °C, [C2] = 0.33 M, IsoparE = 5 mL, C6 / C2(molar ratio) = 0.6 in liquid, H2 / C2 (molar ratio) = 0.0016 in liquid, run time = 90 mins max (5,400 s), Quench time = time needed to uptake 90 psi of ethylene; the faster the quench time, the more active the catalyst is. All catalysts are 45 µmol Zr or Hf / g SMAO.

[0126] Table 4 provides a comparison of the activity and C6 wt. % produced at various temperatures. Table 486020-WO-PCT / DOW 86020 WO*Slurry PPR conditions: Temp. = 100 or 80 °C, IsoparE = 5 mL, C6 / C2 (molar ratio) = 0.6 in liquid, H2 / C2(molar ratio) = 0.0016 in liquid, run time = 90 mins max (5400 s), Quench time = time needed to uptake 90 psi of ethylene; the faster the quench time, the more active the catalyst is. All catalysts are 45 µmol Zr or Hf / g SMAO.

[0127] Generally, lesser quench times indicate greater activity. For example, high activity in slurry PPR experiments is deemed to occur when quench times are ≤ 1,500 seconds when using catalyst charges of ≤ 25 nmol in formulations of 45 µmol Zr or Hf / g SMAO, or lower. The quench time is the time it takes to consume 90 psig of ethylene during the experiment, where the faster the time, the more active the catalyst.

[0128] Under process relevant high density conditions at 100 °C and 80 °C (as is shown in Table 2, Table 3, and Table 4), each of the examples have excellent activity (fast quench times). In specific, examples E1–E4 E7–E9, E11, and E13-E14 show very high activity for the catalyst systems of the present disclosure. Similar results are shown at 80 ºC (Table 4).

[0129] Optimal activity was observed for those catalysts possessing an ortho-substituted aryl amine group on the 2-benzothiazole position such as, but not limited to, 2,6-dimethylphenyl and 1-naphthyl (S-1, S-4, and S-7 through S-9). In addition, high activity was observed for the catalysts that have cyclopentadienyl ligands bearing mono-methyl and mono-n-butyl substitution (S-3, S- 4, S-8, and S-9. However, far lower activity (significantly slower quench times) were observed for catalysts possessing an adamantyl substituted amine on the 2-benzothiazole (S-5 and S-6), regardless of substitution on the cyclopentadienyl ligand.

[0130] Moreover, based on the GPC analysis of the polyethylene-hexene copolymers produced, under these slurry process conditions at 100 °C, several of the supported catalysts of the present disclosure produce polyethylene with ultra-low hexene incorporation (0.0 – 0.4 wt% in E1-E2 and E7-E10). The supported catalysts of the present disclosure also produce polymer with a range of Mwthat trends with the identity of the N-aryl amine. For instance, S-1, S-4, and S-9, bearing a 2,6- dimethylphenyl group on the amine moiety, produced ethylene / hexene copolymers in E1, E4, and E9 with significantly lower Mw (<7,000 g / mol) than S-10 (47,800 g / mol). S-2, -3, -7, -8, and -10, which have a phenyl or naphthyl group on the amine moiety, produced ethylene / hexene copolymers in E2, E3, E7, E8, and E10 respectively with higher weight average polymer86020-WO-PCT / DOW 86020 WO molecular weights of 20,000 – 50,000 g / mol. Finally, S-5 and -6, having a bulky adamantyl amine group, produced polymers in E5 and E6 with high Mw(100,000 and 600,000 g / mol) and Mz(> 1.5 MM g / mol).

[0131] Furthermore, based on the GPC analysis of the polyethylene-hexene copolymers produced at 80 °C under these slurry process conditions, all of the supported catalysts in E11-E14 produce polyethylene with ultra-low hexene incorporation (0.0 – 0.9 wt%), and, notably, these hexene incorporation values are lower than their corresponding values at the higher 100 °C temperature condition. S-5 has higher hexene incorporation (1.7 wt%) at 100 °C, and conversely, even higher incorporation (2.6 wt%) at 80 °C. For values listed as 0.0 wt% in the tables above, the level of 1-hexene incorporation was either not measurable and / or below the detection limit of the GPC used for analysis.

[0132] The high activity of these supported catalysts combined with the range of Mw capability and ultra-low hexene incorporation, and the fact that these trends in activity and hexene incorporation are retained and in some cases (E13-E14) improved upon at lower process temperatures (i.e., 80 °C), offers a resin with potentially advantageous properties for both single and multi-catalyst applications using single and / or multi-reactor configurations, as well as desirable process flexibility as a result of favorable temperature response.

[0133] While particular embodiments of the present disclosure have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the disclosure. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this disclosure.

Claims

86020-WO-PCT / DOW 86020 WO CLAIMS 1. A method of making polyethylene comprising: polymerizing in a slurry p3hase reactor ethylene monomer and optionally at least one C3 to C201-alkene comonomer in the presence of a suspension comprising a catalyst system in an inert hydrocarbon liquid, the catalyst system comprising a procatalyst complex having a structure according to Formula (I):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 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; Q is a monoanionic spectator ligand selected from (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C5-C30)aryl, and (C3-C30)heteroaryl; wherein Q is different from each X;86020-WO-PCT / DOW 86020 WO 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.

2. The method of claim 1, wherein: each X is independently selected from (C1−C10)alkyl, (C6−C20)aryl, or a halogen; and R1is a (C1−C30)alkyl, or a (C6−C30)aryl.

3. The method of claim 1 or 2, wherein R2and R3are covalently linked to form an aromaticring, and the procatalyst has a structure according to Formula (II):where each R1, Q, X, n, and M are defined as in Formula (I); and each R4, R5, R6, and R7are independently (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, (C6-C40)aryl, (C3-C40)heteroaryl, a halogen, or –H.86020-WO-PCT / DOW 86020 WO4. The method of any one of claims 1 to 3, wherein Q is chosen from formulas:wherein: R8, R9, and R10 are independently chosen from (C1−C30)hydrocarbyl, (C1- C50)heterohydrocarbyl, (C6–C30)aryl, or (C3–C30)heteroaryl; R11 R12, R13, and R14, are independently chosen from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl,86020-WO-PCT / DOW 86020 WO −Si(RC)3, −Ge(RC)3, −N(RN)2, −ORC, and –H, wherein each RNand RCis independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, and –H, and optionally R11 and R12, or R11 and R13, or R11 and R14, R13and R14, or R12and R13, or R12and R14may be covalently connected to form an aromatic ring or non-aromatic ring; and R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, and R26 are independently chosen from –H, (C1-C30)hydrocarbyl, (C1-C30)heterohydrocarbyl, (C6–C30)aryl, (C3–C30)heteroaryl, −Si(RC)3, or -Ge(RC)3; And optionally R15and R16, R16and R17, R17and R18, R18and R19, R20and R21, R21and R22, R22 and R23, R24 and R25, or R25 and R26 are covalently linked to form one or more ring or multi-ring structures.

5. The method of any preceding claim, wherein Q is Formula (V) or Formula (VI).

6. The method of claim 5, wherein R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, and R26 are independently chosen from –H and (C1-C12)alkyl.

7. The method of any one of claims 1-6, wherein R1 is a phenyl, 2,6-dimethylphenyl, 1- naphthyl, 2-naphthyl, or adamantyl.

8. The method of any one of the claims 3-6, wherein R4 is a phenyl, 2,6- dimethylphenyl, or 2,4,6-trimethylphenyl.

9. The method of any one of claims 3-6, wherein the structure (II) is represented by anyone of the structures (IIa) through (IIl):86020-WO-PCT / DOW 86020 WOstructure (IIb);structure (IId);(IIh);86020-WO-PCT / DOW 86020 WO -50-re (IIl); 10. The method of any preceding claim, wherein the catalyst system is a supported catalyst system comprising: the procatalyst; an activator; and a support.

11. The method of claim 10, wherein the activator comprises methylaluminoxane.

12. The method of claim 10 or 11, wherein the support comprises silica or fumed silica.86020-WO-PCT / DOW 86020 WO 13. The method of claims 10 to 12, wherein the molar ratio of metal in the activator to Group IV metal in the structure represented by Formula I or Formula II is from 3,500 : 1 to 0.5 :

1.

14. The method of any preceding claim, wherein the inert hydrocarbon liquid comprises mineral oil, a hydrocarbon solvent, or a combination thereof.

15. A polyethylene produced from the method of any preceding claim.

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