Supported BIS(phenoxy-phenyl) catalysts for slurry-phase polymerization processes

Abstract

The present disclosure provides for a supported bis(phenoxy-phenyl) (Sup-BPP) catalysts for production of polyethylene in a slurry-phase polymerization process. The Sup-BPP catalysts of the present disclosure include an inert support in the presence of an aluminoxane compound, where the aluminoxane compound functions as a binding agent. The Sup-BPP can be mixed with the support and the binder in an inert hydrocarbon. The Sup-BPP catalyst can be used for ethylene / alpha-olefin co-polymerizations in a slurry-phase reactor.

Description

[0001] SUPPORTED BIS(PHENOXY-PHENYL) CATALYSTS FOR SLURRY-PHASE POLYMERIZATION PROCESSES

[0002] Technical Field

[0003] The present disclosure relates to bis (phenoxy- phenyl) catalysts and in particular to supported bis (phenoxy-phenyl) catalysts for polyethylene production in a slurry-phase polymerization process.

[0004] Background

[0005] Polyethylene resins are used in a wide variety of applications. In producing these resins, the polyethylene polymerization process can be varied in a number of respects to produce a wide variety of physical properties that render the various resins suitable for use in different applications. In a slurry-phase polymerization process, the ethylene monomers and, optionally, one or more co-monomers are present in the slurry phase, along with a catalyst system, which typically consists of transition metal compounds supported on a solid material, such as silica or aluminum oxide. Selection of the catalyst systems used in the polymerization process is an important factor contributing to the characteristics and properties of polyethylene resins.

[0006] In the slurry-phase polymerization process, an activated catalyst, monomer(s), and a liquid diluent (often an inert hydrocarbon like isobutane or hexane) are combined in a reactor, where the catalyst initiates the polymerization reaction to form the polymer chains. As the polymer chains grow, they precipitate out of the solution, forming a slurry of solid polymer particles suspended in the liquid diluent. The solid polymer particles are separated from the liquid diluent through a filtration or centrifugation process, and then dried to remove residual solvent. The slurry-phase polymerization process can provide for the high production of polymer particles having well-defined particle morphology and polymer properties.

[0007] As appreciated in the art, slurry phase reactors offer advantages such as helping to prevent overheating and control the reaction rate. The catalyst systems for producing polyethylene in such slurry phase reactors typically include chromium-based catalyst systems, Ziegler-Natta catalyst systems, and / or molecular (either metallocene or non-metallocene (molecular)) catalyst systems. Despite the research efforts in developing catalyst systems suitable for olefin polymerization in slurry phase reactors, such as polyethylene polymerization, there is still a need to increase the efficiencies and ethylene selectivity of catalyst systems that are capable of producing polymers with high molecular weights and narrow molecular weight distributions and where the catalyst system also has a high selectivity towards ethylene, especially those that can take advantage of slurry phase reactor systems.

[0008] Summary

[0009] The present disclosure addresses the above identified needs in the art by providing supported bis (phenoxy-phenyl) (Sup-BPP) catalysts for production of polyethylene in a slurryphase polymerization process. The Sup-BPP catalysts of the present disclosure include an inert support in the presence of an aluminoxane compound, where the aluminoxane compound functions as a binding agent, as discussed herein. By way of example, the bis (phenoxy-phenyl) catalyst is mixed with support (e.g., silica, fumed silica) and the binder (e.g., an aluminoxane compound such as MAO) in an inert hydrocarbon (e.g. an inert hydrocarbon such as toluene). The slurry can be dried, either under reduced pressure or spray dried, to produce the Sup-BPP catalyst. The Sup-BPP catalyst can be used for ethylene / alpha-olefin co-polymerizations in a slurry phase reactor.

[0010] The Sup-BPP catalysts of the present disclosure are of particular interest due to their higher ethylene selectivity. This is beneficial for making bimodal ethylene / alpha-olefin copolymers as the high ethylene selectivity of the Sup-BPP catalysts of the present disclosure gives much more flexibility and freedom of design for the resin in terms of density splits of the polymer and maintaining good properties at higher densities.

[0011] Embodiments of the present disclosure provide for a supported bis(phenoxy-phenyl) (Sup-BPP) catalyst that includes a compound of Formula (I):

[0012]

[0013] (I)

[0014] In Formula (I), M is scandium (Sc), yttrium (Y) or a lanthanide metal. X is a ligand chosen from (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -CH2Si(Rc)3-Q(ORc)Q, -Si(Rc)3-Q(ORc)Q. -OSi(Rc)3-o(ORc)Q, -CH2Ge(Rc)3-Q(ORc)Q, -Ge(Rc)3-Q(ORc)Q, -P(RC)2-W(ORC)W, -P(O)(RC)2-W(ORC)W, -N(RC)2, -NH(RC), -N(Si(Rc)3)2, -NRcSi(Rc)3, -NHSi(Rc)3, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3. -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=CH(RC), -N=CH2, -N=P(RC)3, -OC(O)RC, -C(O)ORC, -N(RC)C(O)RC, -N(Rc)C(O)H, -NHC(O)Rc, -C(O)N(Rc)2, -C(O)NHRc, -C(O)NH2, a halogen, B(RY)4, A1(RY)4, or Ga(RY)4. or a hydrogen, where each Rcis independently a substituted or unsubstituted (Ci-C3o)hydrocarbyl, or a substituted or unsubstituted (Ci-C3o)heterohydrocarbyl. Each of subscript Q is 0, 1, 2 or 3, and each W is 0, 1, or 2. Each RYis -H,

[0015] (Ci-C3o)hydrocarbyl, or halogen atom. Each T is independently a Lewis Base, and n is 0, 1, or 2. When n is 1, X and T are optionally linked and when n is 2, X and one of T are optionally linked. The metal-ligand complex (compound of Formula (I)) is overall charge-neutral.

[0016] Preferably, M is Sc or Y. Most preferably, M is Sc.

[0017] In the compound of Formula (I), each Z is independently chosen from -O-, -S-, - N(RN)-, or -P(Rp)-, where the dotted line optionally defines a dative bond. In addition, R1and R16are independently selected from the group consisting of (Ci-C4o)hydrocarbyl,

[0018] (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3. RCS(O)-, RCS(O)2-, -N=C(RC)2, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-. (RC)2NC(O)-, or halogen. More specifically, R1and R16can be chosen from radicals having Formula (II) and radicals having Formula (III):

[0019]

[0020] where each of R17–24, and R25–33is independently chosen from -H, (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2- (RC)2C=N-, RCC(O)O- RCOC(O)-, RCC(O)N(RN)-, (RC)2NC(O)-, or halogen. For the various embodiments, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15are independently selected from -H, (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(RN)2-ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-(Rc)2C=N-, (RC)2P=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-, and halogen. For the various embodiments, L is (Ci-C4o)hydrocarbylene or (Ci-C4o)heterohydrocarbylene; and each Rc, Rp, and RNin formula (I) is independently a (Ci-C3o)hydrocarbyl,

[0021] (Ci-C3o)heterohydrocarbyl, or -H. The Sup-BPP catalyst further includes an inert support, where the compound of Formula (I) is supported on the inert support, and, optionally, an aluminoxane to form the Sup-BPP catalyst.

[0022] Detailed Description

[0023] The present disclosure addresses the above identified needs in the art by providing supported bis (phenoxy-phenyl) (Sup-BPP) catalysts for production of polyethylene in a slurryphase polymerization process. The Sup-BPP catalysts of the present disclosure include an inert support in the presence of an aluminoxane compound, where the aluminoxane compound functions as a binding agent, as discussed herein. By way of example, the bis (phenoxy-phenyl) catalyst is mixed with support (e.g., silica, fumed silica) and the binder (e.g., an aluminoxane compound such as MAO) in an inert hydrocarbon (e.g. an inert hydrocarbon such as toluene). The slurry can be dried, either under reduced pressure or spray dried, to produce the Sup-BPP catalyst. The Sup-BPP catalyst can be used for ethylene / alpha-olefin co-polymerizations in a slurry-phase reactor.

[0024] The Sup-BPP catalysts of the present disclosure are of particular interest due to their higher ethylene selectivity. This is beneficial for making bimodal ethylene / alpha-olefin copolymers as the high ethylene selectivity of the Sup-BPP catalysts of the present disclosure gives much more flexibility and freedom of design for the resin in terms of density splits of the polymer and maintaining good properties at higher densities.

[0025] Specific embodiments of the supported bis(phenoxy-phenyl) (Sup-BPP) catalyst will now be described. It should be understood that the Sup-BPP catalyst 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.

[0026] Common abbreviations are listed below:

[0027] R, Z, Mol, X and n: as defined herein for their respective Formula: Me = methyl; Et = ethyl; Ph = phenyl; Bn = benzyl; i-Pr = iso-propyl; t-Bu = tert-butyl; t-Oct = tert-octyl (2,4,4-trimethylpentan-2-yl); Tf = trifluoromethane sulfonate; CV = column volume (used in column chromatography); EtOAc = ethyl acetate; TEA = triethylaluminum; MAO = methylaluminoxane: MMAO = modified methylaluminoxane; LiCH2TMS = (trimethylsilyl)methyllithium; TMS = trimethylsilyl; Pd(AmPhos)C12 = Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II); Pd(AmPhos) = Chloro(crotyl)(di-tert-butyl(4-dimethylaminophenyl)phosphine)palladium(II); Pd(dppf)C12 = [1,1’-Bis(diphenylphosphino)ferrocene]palladium(II) dichloride; ScCl3= scandium(III) chloride: PhMe = toluene; THF = tetrahydrofuran; CH2Cl2= dichloromethane; DMF = N, N-dimethylformamide; EtOAc = ethyl acetate; Et2O = diethyl ether; MeOH = methanol; NH4Cl = ammonium chloride; MgSO4 = magnesium sulfate; Na2SO4 = sodium sulfate; NaOH = sodium hydroxide; brine = saturated aqueous sodium chloride; SiO2 = silica; CDCl3= chloroform-D; GC = gas chromatography; LC = liquid chromatography; NMR = nuclear magnetic resonance; MS = mass spectrometry; mmol = millimoles; mL = milliliters; Mol = molar: min or mins = minutes; h or hrs = hours; d = days; TLC; thin layered chromatography; rpm = revolution per minute; rt = room temperature (23 °C).

[0028] The term “independently selected” is used herein to indicate that, for example, the R groups, such as, R1, R2, R3, R4, and R5, can be identical or different (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.). A chemical name associated with an R group is intended to convey the chemical structure that is recognized in the art as corresponding to that of the chemical name. Thus, chemical names are intended to supplement and illustrate, not preclude, the structural definitions known to those of skill in the art.

[0029] 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 (C| -C5o)alkyl is an alkyl group having from 1 to 50 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 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 “(C] -C5o)alkyl substituted with exactly one group Rs, where Rsis phenyl (-CeHs)” may contain from 7 to 56 carbon atoms. Thus, in general when a chemical group defined using the “(Cx-Cy)” parenthetical is substituted by one or more carbon 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.

[0030] 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. “Hydrogen” and “ -H” are interchangeable, and unless clearly specified have identical meanings.

[0031] The term “(C| -C5Q)hydrocarbyl” means a hydrocarbon radical of from 1 to 50 carbon atoms and the term “(Cj -C5o)hydrocarbylene” means a hydrocarbon diradical of from 1 to 50 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. In this disclosure, a (Ci -C5o)hydrocarbyl may be an unsubstituted or substituted (Ci -C5o)alkyl, (C3 -C5Q)cycloalkyl, (C3 -C2o)cycloalkyl-(Ci -C2Q)alkylene, (Cg -C4o)aryl, or (Cg -C2o)aryl-(C -C2o)alkylene (such as benzyl (-CH2-C5H5)).

[0032] The terms “(Ci -C5o)alkyl” and “(Ci -C i^alkyl” mean a saturated straight or branched hydrocarbon radical of from 1 to 50 carbon atoms and a saturated straight or branched hydrocarbon radical of from 1 to 18 carbon atoms, respectively, that is unsubstituted or substituted by one or more Rs. Examples of unsubstituted (Ci -C5o)alkyl are unsubstituted (Ci -C2o)alkyl; unsubstituted (Ci -Cio)alkyl; unsubstituted (Ci -Cs)alkyl; methyl; ethyl; 1 -propyl; 2-propyl; 1 -butyl; 2-butyl; 2- methylpropyl; 1,1 -dimethylethyl; 1 -pentyl; 1 -hexyl; 1 -heptyl; 1-nonyl; and 1 -decyl. Examples of substituted (Ci -C4o)alkyl are substituted (Ci -C2o)alkyl, substituted (Ci -Cio)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 -C4o)alkyl substituted by one Rs, which is a (Ci -C5)alkyl, respectively. Each (Ci -Cs)alkyl may be methyl, trifluoromethyl, ethyl, 1 -propyl, 1 -methylethyl, or 1,1 -dimethylethyl.

[0033] The term “(Cfj-C^oJaryl” means an unsubstituted or substituted (by one or more Rs) monocyclic, bicyclic, 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. 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 (Ce -Cso)aryl include: unsubstituted (Ce -Czo)aryl, unsubstituted (Ce -Cis)aryl; 2-(Ci -C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (Ce -C4o)aryl include: substituted (Ci -C2o)aryl; substituted (Ce -Cis)aryl; 2,4-bis([C2o]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-l-yl.

[0034] The term “(C3-C5o)cycloalkyl” means a saturated cyclic hydrocarbon radical of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more Rs. Other cycloalkyl groups (e.g., (Cx -Cy)cycloalkyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more Rs. Examples of unsubstituted (C3 -C4o)cycloalkyl are unsubstituted (C3 -C2o)cycloalkyl, unsubstituted (C3 -Cio)cycloalkyl. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3 -C4o)cycloalkyl are substituted (C3 -C2o)cycloalkyl, substituted (C3 -Cio)cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0035] Examples of (Cj-C5Q)hydrocarbylene include unsubstituted or substituted (Cg-C5o)arylene, (C3-C5o)cycloalkylene, and (Cj-C5o)alkylene (e.g., (Ci-C^O / alkylene). The diradicals may be on the same carbon atom (e.g., -CH2 -) or on adjacent carbon atoms (i.e., 1,2-diradicals), or are spaced apart by one, two, or more than two intervening carbon atoms (e.g., 1,3- diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1.3-, 1,4-, or an a, o-diradical, and others a 1,2-diradicaL The a, co-diradical is a diradical that has maximum carbon backbone spacing between the radical carbons. Some examples of (C2-C2o)alkylene a, co-diradicals include ethan- 1,2-diyl (i.e. -CH2CH2-), propan- 1,3-diyl (i.e. -CH2CH2CH2-), 2-methylpropan-l,3-diyl (i.e. -CH2CH(CHs)CH2-). Some examples of (Ce -Csojarylene a.co-diradicals include phenyl- 1,4-diyl, napthalen-2,6-diyl, or napthalen-3,7-diyl.

[0036] The term “(C^-C5o)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. Examples of unsubstituted (C |-C5()) lkylene are unsubstituted (C|-C2o)alkylene, including unsubstituted -CH2CH2-, -(CH2)3~, -(CH2)24~, -(CH2)5- -(CH2)6 - -(CH2)7- -(CH2)8- -CH2C*HCH3, and -(CH2)4C*(H)(CH3), in which “C*” denotes a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (Ci-CgoJalkylene are substituted (Cj-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 (Ci-Cig)alkylene, examples of substituted (Ci-C5o)alkylene also include 1,2-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. The term “(C3 -C5o)cycloalkylene” means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 50 carbon atoms that either is unsubstituted or is substituted by one or more Rs.

[0037] 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)z, Si(Rc)2, P(Rp), N(RN), -N=C(RC)2, -Ge(Rc)2-, -Si(Rc)-, boron (B), aluminum (Al), gallium (Ga). or indium (In), where each Rcand each Rpis unsubstituted (Ci -Cis)hydrocarbyl or -H, and where each RNis unsubstituted (Ci-Ci8)hydrocarbyl. The term “heterohydrocarbon” refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. The term “(C i-C5o)heterohydrocarbyl” means a heterohydrocarbon radical of from 1 to 50 carbon atoms, and the term “(Ci-C5o)heterohydrocarbylene” means a heterohydrocarbon diradical of from 1 to 50 carbon atoms. The heterohydrocarbon of the (Cj-C5o)heterohydrocarbyl or the (C i-C5o)heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl may be on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene may be on a single carbon atom or on a single heteroatom.

[0038] Additionally, one of the two radicals of the diradical may be on a carbon atom and the other radical may be on a different carbon atom; one of the two radicals may be on a carbon atom and the other on a heteroatom; or one of the two radicals may be on a heteroatom and the other radical on a different heteroatom. Each (Ci -C5o)heterohydrocarbyl and (Ci -C5o)heterohydrocarbylene may be unsubstituted or substituted (by one or more Rs), aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including mono-and poly-cyclic, fused and non-fused polycyclic), or acyclic.

[0039] The (Ci -C5o)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (Ci -C5o)heterohydrocarbyl include (Ci -C5o)heteroalkyl, (Cl -C50)hydrocarbyl-O -, (Ci-C5o)hydrocarbyl-S -, (Ci-C5o)hydrocarbyl-S(0) (Ci-C5o)hydrocarbyl-S(0)2 -, (C C5o)hydrocarbyl-Si(Rc)2 -, (Cj-C5o)hydrocarbyl-N(RN) -, (Ci-C5o)hydrocarbyl-P(Rp) -, (C2-C5o)heterocycloalkyl, (C2-C |9)heterocycloalkyl- (Cj-C2o)alkylene, (C3-C2o)cycloalkyl-(Ci-Ci9)heteroalkylene, (C2-C]9 heterocycloalkyl- (C |-C2())heteroalkylene, (C C5o)heteroaryl, (C | -C 19)heteroaryl-(C | -C20? alkylene, (Cg-C2o)aryl- (Cj-Ci9)heteroalkylene, or (C 1 -C 19)heteroaryl- (C ] -C2o)heteroalkylene. The term “(Ci-C5o)heteroaryl” means an unsubstituted or substituted (by one or more Rs) mono-, bi-, or tricyclic heteroaromatic hydrocarbon radical of from 1 to 50 total carbon atoms and from 1 to 10 heteroatoms. A monocyclic hetero aromatic 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 (Ci -Ci2)heteroaryl) are defined in an analogous manner as having from x to y carbon atoms (such as 1 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 monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms, where h is the number of heteroatoms and may be 1, 2, 3. or 4; and each heteroatom may be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol- 1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-l-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-l-yl; l,3,4-oxadiazol-2-yl; l,3,4-thiadiazol-2-yl; tetrazol- 1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring monocyclic heteroaromatic hydrocarbon radical has 6 minus h carbon atoms, where 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 hetero aromatic 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-l-yl; and benzimidazole- 1-yl. Examples of the fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin- 1-yl. The tricyclic heteroaromatic hydrocarbon radical can be a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6, 6,6-ring system. An example of the fused 5,6,5-ring system is 1,7- dihydropyrrolo[3,2-f]indol-l-yl. An example of the fused 5, 6,6-ring system is lH-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. The term “(Ci-C5o)heteroalkyl” means a saturated straight or branched chain radical containing one to fifty carbon atoms and one or more heteroatom. The term “(Cj-C5o)heteroalkylene” means a saturated straight or branched chain diradical 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.

[0040] Examples of unsubstituted (C2 -C4o)heterocycloalkyl include unsubstituted (C2 -C2o)heterocycloalkyl, unsubstituted (C2 -Cio)heterocycloalkyl, aziridin-l-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-l-yl, tetrahydrothiophen-S, S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0041] 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 anionic form of the halogen atom: fluoride (F“), chloride (Cl-), bromide (Br“), or iodide (I-).

[0042] 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 be present in substituents Rs. The term “unsaturated” means containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or (in hetero atom-containing groups) one or more carbon-nitrogen double bonds, carbon-phosphorous double bonds, or carbon-silicon double bonds, not including double bonds that may be present in substituents Rs, if any, or in aromatic rings or heteroaromatic rings, if any.

[0043] The term “lanthanide metal” includes elements 57 through 71 (lanthanum (La) to lutetium (Lu)).

[0044] Embodiments of the present disclosure provide for a supported bis(phenoxy-phenyl) (Sup-BPP) catalyst that includes a compound of Formula (I):

[0045]

[0046] (I)

[0047] In Formula (I), M is scandium (Sc) or yttrium (Y) or a lanthanide metal, X is a ligand chosen from (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -CH2Si(Rc)3-Q(ORc)Q, -Si(Rc)3-Q(ORc)Q. -OSi(Rc)3-Q(ORc)Q, -CH2Ge(Rc)3-Q(ORc)Q, -Ge(Rc)3-Q(ORc)Q, -P(RC)2-W(ORC)W, -P(O)(RC)2-W(ORC)W, -N(RC)2, -NH(RC), -N(Si(Rc)3)2, -NRcSi(Rc)3, -NHSi(Rc)3, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3. -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=CH(RC), -N=CH2, -N=P(RC)3, -OC(O)RC, -C(O)ORC, -N(RC)C(O)RC, -N(Rc)C(O)H, -NHC(O)Rc, -C(O)N(Rc)2, -C(O)NHRc, -C(O)NH2, a halogen, B(RY)4, A1(RY)4, or Ga(RY)4. or a hydrogen, where each Rcis independently a substituted or unsubstituted (Ci-C3o)hydrocarbyl, or a substituted or unsubstituted (Ci-C3o)heterohydrocarbyl. Each of subscript Q is 0, 1, 2 or 3, and each W is 0, 1, or 2. Each RYis -H,

[0048] (Ci-C3o)hydrocarbyl, or halogen atom. Each T is independently a Lewis Base, and n is 0, 1, or 2. When n is 1, X and T are optionally linked and when n is 2, X and one of T are optionally linked. The metal-ligand complex (compound of Formula (I)) is overall charge-neutral.

[0049] Preferably, M is Sc or Y. More preferably, M is Sc.

[0050] In embodiments, the dotted lines are optionally dative bonds between the metal center, M and the group Z. In some embodiments, one of the dotted lines connecting Z and Mis dative and the other dotted line does not form a dative bond between Z and M. In various embodiments, both dotted lines form dative bonds between groups Z and M.

[0051] In the compound of Formula (I), each Z is independently chosen from -O-, -S-, — N(RN)—, or -P(Rp)-, where the dotted line optionally defines a dative bond. In addition, R1and R16are independently selected from the group consisting of (Ci-C4o)hydrocarbyl,

[0052] (Ci-C4o)heterohydrocarbyl. -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(RN)2. -ORC. -SRC, -NO2, -CN. -CF3, RCS(O)-, RCS(O)2- -N=C(RC)2, RCC(O)O- RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-or halogen. More specifically, for the compound of Formula (I) R1and R16can be chosen from radicals having Formula (II) and / or radicals having Formula (III):

[0053] where each of R17–24, and R25–33is independently chosen from -H, (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-. RCS(O)2- (RC)2C=N- RCC(O)O- RCOC(O)-, RCC(O)N(RN)-, (RC)2NC(O)-, or halogen. For the various embodiments, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15are independently selected from -H, (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3. -Ge(Rc)3. -P(Rp)2. -N(RN)2-ORC, -SRC, -NO2, -CN, -CF3. RCS(O)-. RCS(O)2-

[0054]

[0055] (RC)2C=N-, (RC)2P=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-, and halogen. Independently each Rc, Rp, and RNin formula (I) are unsubstituted (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, or -H. For the various embodiments, L is (Ci-C4o)hydrocarbylene or (C i -C4o)heterohydroc arbylene.

[0056] The groups R1and R16in the compound of Formula (I) can be chosen independently of one another. For example, R1may be chosen from a radical having formula (II) or (III) and R16may be a (Cl -C40)hydrocarbyl; or R1may be chosen from a radical having formula (II) or (III) and R16may be chosen from a radical having formula (II) or (III) the same as or different from that of R1. Both R1and R16may be radicals having formula (II), for which the groups R1724are the same or different in R1and R16. In other examples, or both R1and R16may be radicals having formula (III), for which the groups R25'33are the same or different in R1and R16.

[0057] The Sup-BPP catalyst further includes an inert support, where the compound of Formula (I) is supported on the inert support, and an aluminoxane to form the Sup-BPP catalyst, each of which will be more fully discussed herein.

[0058] In some embodiments, at least one of R1and R16is a radical having formula (II), where R18and R23are (Ci-C2o)hydrocarbyl, -Si[(Ci-C2o)hydrocarbyl]3, or -Ge[(Ci-C2o)hydrocarbyl]3. In additional embodiments, at least one of R1and R16is a radical having formula (II), where R19 and R22are (Ci-C2o)hydrocarbyl, -Si[(Ci-C2o)hydrocarbyl]3, or -Ge[(Ci-C2o)hydrocarbyl]3. For such various embodiments, R17, R20, R21and R24are -H.

[0059] In some embodiments, at least one of R1and R16is a radical having formula (III), where R26and R33are (Ci-C2o)hydrocarbyl, -Si[(Ci-C2o)hydrocarbyl]3, or -Ge[(Ci-C2o)hydrocarbyl]3. In additional embodiments, at least one of R1and R16is a radical having formula (III), where R27and R31are (Ci-C2o)hydrocarbyl. -Si[(Ci-C2o)hydrocarbyl]3, or -Ge[(Ci-C2o)hydrocarbyl]3. For such various embodiments, R25, R28, R29, R30and R33are -H.

[0060] In some embodiment of the compound of Formula (I), R1and R16can be chosen from 3.5-di-tert-butylphenyl; 2,4,6-trimethylphenyl; 2,4,6-triisopropylphenyl; 3,5- diisopropylphenyl; carbazolyl; carbazol-9-yl, 1,2,3,4-tetrahydrocarbazolyl; 1,2, 3, 4, 5, 6, 7, 8- octahydrocarbazolyl; 3.6-bis-(3,5-di-tert-butylphenyl)carbazol-9-yl: 3,6-bis-(2,4,6- trimethylphenyl)carbazol-9-yl); 3.6-bis-(2,4,6-triisopropylphenyl)carbazol-9-yl; 2,7- di(tertiarybutyl)-carbazol-9-yl; 2,7-di(tertiary-octyl)-carbazol-9-yl; 2,7-diphenylcarbazol-9-yl; 2,7-bis(2,4,6-trimethylphenyl)-carbazol-9-yl anthracenyl; 1,2,3,4-tetrahydroanthracenyl; 1,2,3,4,5,6,7,8-octahydroanthracenyl; phenanthrenyl; 1,2,3,4,5,6,7,8-octahydrophenanthrenyl; 1,2,3,4-tetrahydronaphthyl; 2,6-dimethylphenyl; 2,6-diisopropylphenyl; 3,5-diphenylphenyl; 1- naphthyl; 2-methyl-l-naphthyl; 2-naphthyl; l,2,3,4-tetra-hydronaphth-5-yl; 1,2, 3, 4- tetrahydronaphth-6-yl; anthracen-9-yl; 1, 2,3,4-tetrahydroanthracen-9-yl; 1,2, 3, 4, 5, 6, 7, 8- octahydroanthracen-9-yl; 1, 2, 3, 4, 5, 6,7,8-octahydrophenanthren-9-yl; indolyl; indolinyl; quinolinyl; 1,2,3,4-tetrahydroquinolinyl; isoquinolinyl; or 1,2,3,4-tetrahydroisoquinolinyl.

[0061] In Formula (I), R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15is independently selected from -H, (Cl-C40)hydrocarbyl, (Cl -C40)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(RP)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2- (RC)2C=N-RcC(O)O-, RcOC(O)-, RcC(O)N(R)-, (Rc)2NC(O)-, and halogen.

[0062] For the various embodiments, in Formula (I) at least one of R8and R9is not -H. In various embodiments, at least one of R8and R9is (Cl-C5)hydrocarbyl. In some embodiments, both R8and R9are (Cl-C5)hydrocarbyl. In some embodiments, R8and R9are methyl. In other embodiments, R8and R9are halogen.

[0063] For the various embodiments, in Formula (I) R6and R11are selected from

[0064] (Ci-C3o)hydrocarbyl, hydrogen, or halogen. For the various embodiments, in Formula (I) R6and R11are halogen. For the various embodiments, in Formula (I) R6and R11are methyl or fluorine (F). Preferably, in Formula (I) R6and R11are F. In some embodiments, R6and R11are

[0065] (Ci-C24)alkyl. In various embodiments, R6and R11independently are chosen from methyl, ethyl, 1 -propyl, 2-propyl (also called iso-propyl), 1,1- dimethylethyl (also called tert-butyl), cyclopentyl, cyclohexyl, 1 -butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. In some embodiments, R6and R11are tert-butyl. In embodiments. R6and R11are -ORC, wherein Rcis

[0066] (Cl-C20)hydrocarbyl, and in some embodiments, Rcis methyl, ethyl, 1- propyl, 2-propyl (also called iso-propyl), or 1,1 -dimethylethyl. In other embodiments, R6and R11are -SiRc3, wherein each Rcis independently (Ci-C2o)hydrocarbyl, and in some embodiments, Rcis methyl, ethyl, 1 -propyl, 2-propyl (also called iso-propyl), or 1,1 -dimethylethyl.

[0067] For the various embodiments, in Formula (I) R3and R14are (Ci-C5)hydrocarbyl.

[0068] Preferably, in Formula (I) R3and R14are Me.

[0069] For the various embodiments, L can be selected from the group of -CH2-, -CH2(CH2)mCH2- where m is from 0 to 3, -CH2Si(Rc)2CH2-, -CH2Ge(Rc)2CH2-, -CH(CH3)CH2C*H (CH3), and -CH2(phen-l,2-di-yl)CH2-, where each Rcin L is

[0070] (Ci-C2o)hydrocarbyl, and “C*” is a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical.

[0071] In some embodiments, any or all of the chemical groups (e.g., X and R1-59) of the compound of Formula (I) may be unsubstituted. In other embodiments, none, any, or all of the chemical groups X and R1-59of the compound 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 and R1-59may 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. In one or more embodiments, Rsis chosen from

[0072] (Ci-C2o)hydrocarbyl, (Ci-C2o)alkyl, (Ci-C2o)heterohydrocarbyl, or (Ci-C2o)heteroalkyl.

[0073] In the compound of Formula (I), L is (Cl -C40)hydrocarbylene or (Cl -C40)heterohydrocarbylene; and each Z is independently chosen from -O-, -S-, -N(RN)-, or - P(Rp)-. In one or more embodiments, L includes from 1 to 10 atoms. In the Formulas (I), (II) and (III), each Rc, Rp, and RNis independently a (C 1 -C30)hydrocarbyl, (Cl -C30)heterohydrocarbyl, or -H.

[0074] In some embodiments of the compound of Formula (I), the L may be chosen from (C3 -C7)alkyl 1,3- diradicals, such as -CH2CH2CH2 -, -CH(CH3)CH2C*H(CH3), -CH(CH3)CH(CH3)C*H(CH3), -CH2C(CH3)2CH2 cyclopentan- 1,3-diyl, or cyclohexan-1,3-diyl, for example. In some embodiments, the L may be chosen from (C4 -Cio)alkyl 1,4-diradicals, such as -CH2CH2CH2CH2 -, -CH2C(CH3)2C(CH?)2CH2 cyclohexane- 1,2-diyldimethyl, and bicyclo[2.2.2]octane-2,3-diyldimethyl, for example. In some embodiments, L may be chosen from (C5 -C12)alkyl 1,5-diradicals, such as - CH2 CH2CH2CH2CH2-, and 1,3-bis(methylene)cyclohexane. In some embodiments, L may be chosen from (C6 -C14)alkyl 1,6-diradicals, such as - CH2CH2CH2CH2CH2CH2- or l,2-bis(ethylene)cyclohexane, for example.

[0075] In one or more embodiments. L is (C2 -C40)heterohydrocarbylene, and at least one of the from 2 to 10 atoms includes a heteroatom. In some embodiments, L is -CH2Ge(Rc)2CH2 -, where each Rcis (Ci -C3o)hydrocarbyl. In some embodiments. L is -CH2Ge(CH3)2CH2 -, -CH2Ge(ethyl)2CH2 -, -CH2Ge(2-propyl)2CH2 -, -CffcGe -butyl CIfc -CH2Ge(cyclopentyl)2CH2 -, or -CH2Ge(cyclohexyl)2CH2 -. In one or more embodiments, L is chosen from -CH2-; -CH2CH2-; - CH2(CH2)mCH2~, where m is from 1 to 3; -C

[0076]

[0077] H2Si(Rc)2CH2-; -CH2Ge(Rc)2CH2-; -CH(CH3)CH2C*H (CH3); and -CH2(phen-l,2-di-yl)CH2~; where each Rcin L is (Ci-C2o)hydrocarbyl.

[0078] Examples of such (Ci-Ci2)alkyl include, but are not limited to methyl, ethyl, 1-propyl, 2-propyl (also called iso-propyl), 1,1 -dimethylethyl, cyclopentyl, or cyclohexyl, butyl, tert-butyl, pentyl, hexyl, heptyl, n-octyl, tert-octyl (also called 2,4,4-trimethylpent-2-yl), nonyl, decyl, undecyl, and dodecyl.

[0079] In some embodiments, in the compound of Formula (I), both R8and R9are methyl. In other embodiments, one of R8and R9is methyl and the other of R8and R9is -H.

[0080] In the compound of Formula (I), X bonds with M through a covalent bond or an ionic bond. In some embodiments, X may be a monoanionic ligand having a net formal oxidation state of -1. Each monoanionic ligand may independently be hydride, (Ci -C4o)hydrocarbyl carbanion, (Ci -C4o)heterohydrocarbyl carbanion, halide, nitrate, carbonate, phosphate, sulfate, HC(O)O“, HC(O)N(H)-, (Ci -C4o)hydrocarbylC(0)0-, (Cl -C40)hydrocarbylC(O)N((Cl - C20)hydrocarbyl)“, (Cl -C40)hydrocarbylC(O)N(H)-, RKRLB", RKRLN“, RK0“, RKS“, RKRLP“ or RMRKRLSi“, where each RK, RL, and RMindependently is hydrogen, (Ci -C4o)hydrocarbyl, or (Ci -C4o)heterohydrocarbyl. or RKand RLare taken together to form a (C2 -C4o)hydrocarbylene or (Ci -C2o)heterohydrocarbylene and RMis as defined above.

[0081] In some embodiments, X is -CH2Si[(Ci-C2o)alkyl]3, (Ci-Ci2)alkyl, or halogen atom. In some embodiments, n is 1, and X and T are linked and selected from the group consisting of:

[0082]

[0083] In further embodiments, X is selected from methyl; ethyl; 1-propyl; 2-propyl; 1 -butyl; 2,2,-dimethylpropyl: trimethylsilylmethyl; phenyl; benzyl; or chloro. X is methyl; ethyl: 1-propyl; 2-propyl; 1-butyl; 2,2,-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chloro. In one embodiment, n is 2 and at least two X independently are monoanionic monodentate ligands. In a specific embodiment, n is 2 and the two X groups join to form a bidentate ligand. In further embodiments, the bidentate ligand is 2,2-dimethyl-2-silapropane-l,3-diyl or 1,3-butadiene.

[0084] In one or more embodiments, each X is independently -(CH2)SiRx3, in which each Rxis independently a (Ci-C2o)alkyl or a (Ci-C2o)heteroalkyl and at least one Rxis (Ci-C2o)alkyl. In some embodiments, when one of Rxis a (Ci -C2o)heteroalkyl, the heteroatom is silica or oxygen atom. In some embodiments, Rxis methyl, ethyl, propyl, 2-propyl, butyl, 1,1 -dimethylethyl (or tert-butyl), pentyl, hexyl, heptyl, n-octyl, tert-octyl, or nonyl.

[0085] In one or more embodiments X is -(CH2)Si(CH3)3. -(CH2)Si(CH3)2(CH2CH3);

[0086] -(CH2)Si(CH3)(CH2CH3)2, -(CH2)Si(CH2CH3)3, -(CH2)Si(CH3)2(n-butyl), -(CH2)Si(CH3)2(n-hexyl), -(CH2)Si(CH3)(n-Oct)Rx, -(CH2)Si(n-Oct)Rx2, -(CH2)Si(CH3)2(2-ethylhexyl), -(CH2)Si(CH3)2(dodecyl), - CH2Si(CH )2CH2Si(CH3)3 (herein referred to as -CH2Si(CH3)2CH2TMS). Optionally, in some embodiments, the compound of Formula (I), exactly two Rxare covalently linked or exactly three Rxare covalently linked. In some embodiments, X is -CH2Si(Rc)3-Q(ORc)Q, -Si(Rc)3-Q(ORc)Q, -OS1(RC)3-Q(ORC)Q, in which subscript Q is 0, 1, 2 or 3 and each Rcis independently a substituted or unsubstituted

[0087] (Cl-C30)hydrocarbyl, or a substituted or unsubstituted (Cl-C30)heterohydrocarbyl. In some embodiments, X is methyl or -CH2SiMe3. In the compound of Formula (I), each T bonds with M through a dative bond or an ionic bond. In one or more embodiments, T is a Lewis base. The Lewis base may be a compound or an ionic species, which can donate an electron pair to an acceptor compound. For purposes of this description, the acceptor compound is M. The Lewis base may be neutral or anionic. In some embodiments, the Lewis base may be a heterohydrocarbon or a hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases includes, but are not limited to, amines, trialkylamines, ethers, cycloethers, or sulfides. An example of anionic hydrocarbon includes, but is not limited to. cyclopentadiene. An example of a neutral hydrocarbon includes, but is not limited to, 1,3-buta- di-ene.

[0088] In one or more embodiments, the Lewis base may be a monodentate ligand that may a neutral ligand. In some embodiments, the neutral ligand may contain a heteroatom. In specific embodiments, the neutral ligand is a neutral group such as RTNRKRL, RKORL, RKSRL, or RTPRKRL, where each RTindependently is hydrogen, [(Ci -Cio)hydrocarbylhSi(Ci -Cio)hydrocarbyl. (Ci -C4o)hydrocarbyl, [(Ci -Cio)hydrocarbylhSi. or (Cl -C40)heterohydrocarbyl and each RKand RLindependently is as previously defined.

[0089] In some embodiments, the Lewis base is (Ci -C2o)hydrocarbon. In some embodiments, the Lewis base is cyclopentadiene or 1,3-buta-di-ene. For the various embodiments, when is 1 or 2 at least one T is (Ci-C2o)heterohydrocarbon, where the hetero atom of the heterohydrocarbon is oxygen.

[0090] In various embodiments, the Lewis base is (Ci -C2o)heterohydrocarbon, wherein the hetero atom of the heterohydrocarbon is oxygen. In some embodiments, T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE). For the various embodiments, when n is 1 or 2, and at least one T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

[0091] In the compound of Formula (I), each Z independently is O, S, N(Ci -C4o)hydrocarbyl, or P(Ci -C4o)hydrocarbyl. In some embodiments, each Z is different. For example, one Z is O and the other Z is NCH3. In some embodiments, one Z is O and one Z is S. In another embodiment, one Z is S and one Z is N(Ci -C4o)hydrocarbyl, (for example, NCH3). In a further embodiment, each Z is the same. In yet another embodiment, each Z is O. In another embodiment, each Z is S. In one or more embodiments, R2, R4, R5, R7, R10, R12, R13, and R15are hydrogen; and each Z is oxygen. In Formula (I), each Z is connected to M via a dotted line. The dotted line defines an optional dative bond. In some embodiments, one of the dotted lines forms a dative bond between Z and M and the second dotted line does not directly connect or bonded Z to M. In various embodiments, each Z forms a dative bond with M. In other embodiments, each Z is not directly connected or bonded to M.

[0092] In specific embodiments of catalyst systems, the compound of Formula (I) may include, without limitation, a complex having the structure of any of Compounds (I) - (V):

[0093] Compound (I)

[0094]

[0095] Compound (II) Compound (III)

[0096] Compound (IV)

[0097] PhMe2Si

[0098]

[0099] Compound (V)

[0100] For the various embodiments, the supported bis(phenoxy-phenyl) catalyst includes an inert support, where the compound of Formula (I) is supported on the inert support. For example, the compound of Formula (I) may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more inert supports. The compound of Formula (I) may be combined with one or more inert supports using one of the support methods well known in the art or as described below.

[0101] As used in the present disclosure, the compound of Formula (I) is in a supported form, for example, when deposited on, contacted with, or incorporated within, adsorbed or absorbed in, or on, one or more inert supports. Suitable inert supports, such as inorganic oxides, include oxides of metals of Group 2, 3, 4, 5, 13 or 14 of the IUPAC periodic table (dated 1 December 2018). In embodiments, inert supports 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 inert support 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, inert supports 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. 0511 665), phyllosilicate, zeolites, talc, clays (e.g., as described in U. S. Patent No.

[0102] 6,034,187), and mixtures of these. For the various embodiments, the inert support is selected from the group consisting of silica, fumed silica, alumina, clay, talc and combinations thereof. In other embodiments, combinations of these inert supports may be used, such as, for example, silica-chromium, silica-alumina, silica-titania, and combinations of these. Additional inert supports may also include those porous acrylic polymers described in European Patent No. 0767 184. Other inert supports may also include nanocomposites described in International Patent Application No. 1999 / 047598; aerogels described in International Patent Application No.

[0103] 1999 / 048605; spherulites described in U. S. Patent No. 5,972,510; and polymeric beads described in International Patent Application No. 1999 / 050311.

[0104] For the various embodiments, the inert support can 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 (pm) to 500 pm. In some embodiments, the inert support 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 pm to 200 pm. In other embodiments, the inert support 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 pm to 100 pm. The average pore size of the inert support is typically from 10 Angstroms (A) to 1,000 A, such as from 50 A to 500 A or from 75 A to 350 A. For the various embodiments, the inert support can have a D50 particle size in a range of 8 to 100 microns or 8 to 50 microns. Preferably the inert support can have a D50 particle size in a range of 8 to 40 microns.

[0105] For the various embodiments, the supported bis(phenoxy-phenyl) catalyst can further, optionally, include an aluminoxane to form the supported bis(phenoxy-phenyl) catalyst. For the various embodiments, the aluminoxane is provided as a binder for the inert support, where the aluminoxane may physically support and disperse the catalyst particles. In this role, the aluminoxane can provide a solid matrix that holds together and / or provides a bridge between the inter supports and catalyst particles, preventing them from agglomerating or settling. Examples of suitable aluminoxane to act as a binding agent can include aluminoxanes selected from the group consisting of an aluminum alkyl, an aluminoxane compound and a combination thereof. In more specific examples, the alkyl aluminum and the aluminoxane are selected from the group consisting of methylaluminoxane (MAO), a modified methylaluminoxane (MMAO), trimethylaluminum (TMA), triethylaluminum (TEA), ethylaluminum sesquichloride (EASC) and combinations thereof. Preferably, the aluminoxane is methylaluminoxane (MAO).

[0106] For the various embodiments, the amount of the aluminoxane used as the binding agent to form the supported bis(phenoxy-phenyl) catalyst can include the following molar ratios of Al to M: the molar ratio of A1: M may be from 1:1 to 5,000:1, or from 1:1 to 2,500:1, or from 1:1 to 2,000:1, or from 1:1 to 1,000:1, or from 1:1 to 500:1, or from 1:1 to 250:1, or from 1:1 to 125:1, or from 1:1 to 100:1, or from 1:1 to 75:1, or from 1:1 to 50:1, or from 1:1 to 25:1, or from 1:1 to 10:1, or from 1:1 to 5:1.

[0107] There are various suitable methods to produce the supported bis(phenoxy-phenyl) catalyst of the present disclosure. In one or more embodiments, methods for producing the supported bis (phenoxy-phenyl) catalyst include contacting the inert support and the aluminoxane (binding agent) with the compound of Formula (I) in an inert hydrocarbon solvent to produce the supported bis (phenoxy-phenyl) catalyst. In some embodiments, the method for producing the supported bis (phenoxy-phenyl) catalyst may include disposing the aluminoxane on the inert support that is then contacted with a solution of the compound of Formula (I) in an inert hydrocarbon solvent. For example, in some embodiments, methods for producing the supported bis(phenoxy-phenyl) catalyst include contacting a spray-dried inert support with the aluminoxane with a solution of the compound of Formula (I) in an inert hydrocarbon solvent. In some embodiments, the inert support with the aluminoxane be included in a slurry, such as, for example a mineral oil slurry.

[0108] In some embodiments, the method for producing the supported bis (phenoxy-phenyl) catalyst may include mixing the inert support, the aluminoxane, and the compound of Formula (I) of the present disclosure to produce a catalyst system precursor. The methods may further include drying the catalyst system precursor to produce the supported bis (phenoxy-phenyl) catalyst. More specifically, the methods may include making a mixture of the compound of Formula (I), the inert support, the aluminoxane, or a combination of these, and an inert hydrocarbon solvent. The inert hydrocarbon solvent may then be removed from the mixture to produce the supported bis (phenoxy-phenyl) catalyst. In embodiments, the removing step may be achieved via conventional evaporating of the inert hydrocarbon solvent from the mixture (i.e., conventional concentrating method), which yields the supported bis(phenoxy-phenyl) catalyst. In other embodiments, the removing step may be achieved by spray-drying the mixture, which produces particles of the spray-dried supported bis (phenoxy- phenyl) catalyst. The drying and / or removing steps may not result in the complete removal of liquids from the resulting supported bis(phenoxy-phenyl) catalyst. That is, the supported bis (phenoxy-phenyl) catalyst may include residual amounts (i.e., from 1 wt.% to 3 wt.%) of the inert hydrocarbon solvent.

[0109] As noted above, the supported bis(phenoxy-phenyl) catalyst of the present disclosure may be utilized in a polymerization processes for forming an ethylene-based polymer, such as polyethylene and polyethylene copolymer resins, via the polymerization of olefins, such as ethylene and, optionally, one or more (C3-C12)a-olefin comonomers in a slurry-phase polymerization reactor under olefin polymerizing conditions, as discussed herein, in the presence of a catalyst system comprising a compound of Formula (I) and one or more inert supports, where the compound of Formula (I) is as provided herein. In embodiments, ethylene, and optionally one or more (C3-C12)a-olefins, may be contacted with the supported bis(phenoxy-phenyl) catalyst of the present disclosure in a slurry-phase polymerization reactor. Examples of slurry-phase polymerization reactors and slurry-phase polymerization conditions can be found in, but not limited to, those described in U. S. Pat. No. 10,344,101 B2. The supported bis(phenoxy-phenyl) catalyst of the present disclosure may be slurried prior to entering the slurry reactor, where such slurries are known in the art, or introduced into the slurry reactor as a dry solid. For example, the supported bis(phenoxy-phenyl) catalyst mixed in mineral oil, or mineral oil and a non-reactive hydrocarbon (e.g., toluene) or mixture of hydrocarbons. In addition to toluene, other suitable diluents may include, but are not limited to, ethylbenzene, xylenes, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof. The slurry may be fed to the slurry phase reactor for the polymerization process and / or the slurry may be dried, e.g., spray dried, prior to being fed to the reactor for the polymerization process.

[0110] The slurry phase polymerization process may utilize the use of known equipment and reaction conditions, such as known polymerization conditions. The polymerization process is not limited to any particular type of slurry phase polymerization system. For example, the polymerization temperature may range from about 0 °C to about 300 °C at atmospheric, subatmospheric, or superatmospheric pressure. In particular, a slurry or solution polymerization system may employ subatmospheric or alternatively superatmospheric pressures, and temperatures in the range of about 40 °C to about 300 °C. Embodiments provide a polymerization process for forming an ethylene-based polymer that includes polymerizing ethylene and optionally one or more (C3-C12) a-olefins in the slurry-phase polymerization reactor under olefin polymerizing conditions, as provided herein, in the presence of the supported bis(phenoxy-phenyl) catalyst of the present disclosure.

[0111] The supported bis(phenoxy-phenyl) catalyst may be fed to the slurry-phase polymerization reactor in neat form (i.e., as a dry solid), as a solution, or as a slurry. For example, in some embodiments, particles of the spray-dried supported bis(phenoxy-phenyl) catalyst may be fed directly to the slurry-phase polymerization reactor. In other embodiments, a solution or slurry of the supported bis(phenoxy-phenyl) catalyst in a solvent, such as an inert hydrocarbon or mineral oil, may be fed to the reactor. For example, the supported bis (phenoxyphenyl) catalyst may be fed to the reactor in an inert hydrocarbon solution and the activator may be fed to the reactor in a mineral oil slurry.

[0112] The supported bis(phenoxy-phenyl) catalyst of the present disclosure can provide for increased polyethylene and polyethylene copolymer resin productivity and efficiency in slurryphase polymerization reactor systems, as seen in the Examples section herein. In addition, the polyethylene and polyethylene copolymer resin produced with the supported bis(phenoxy-phenyl) catalyst of the present disclosure can exhibit additional advantageous polymer properties including linear low-to-high density, while also having higher native molecular weights.

[0113] In embodiments, the reactor temperature of the slurry-phase polymerization reactor is from 60 °C to 150 °C. For example, the reactor temperature of the slurry-phase polymerization reactor may be from 60 °C to 120 °C, from 60 °C to 110 °C, from 60 °C to 100 °C, from 60 °C to 90 °C, from 70 °C to 150 °C, from 70 °C to 120 °C, from 70 °C to 110 °C, from 70 °C to 100 °C, from 70 °C to 90 °C, from 80 °C to 150 °C, from 80 °C to 120 °C, from 80 °C to 110 °C, from 80 °C to 100 °C, from 80 °C to 90 °C, from 100 °C to 150 °C. from 100°C to 120 °C, or from 100 °C to 110 °C. Generally, the slurry-phase polymerization reactor may be operated at the highest temperature feasible, taking into account the melting temperature of the polymer product within the reactor. Regardless of the process used to make the polyethylene or the polyethylene copolymer resin, the reactor temperature should be below the melting temperature of the polymer product. As a result, the upper temperature limit may be the melting temperature of the polymer product.

[0114] In embodiments, the reactor pressure of the slurry-phase polymerization reactor is from 1000 kilopascal (kPa) to 10,000 kPa. For example, the reactor pressure of the slurry-phase polymerization reactor may be from 1000 kPa to 9,500kPa, from 1000 kPa to 9,000kPa, from 1000 kPa to 8,500kPa, from 1000 kPa to 8,000kPa, from 1000 kPa to 7,500kPa, from 1000 kPa to 7,000kPa, from 1000 kPa to 6,500kPa, from 1000 kPa to 6,000kPa, from 1000 kPa to 5,500kPa, from 1000 kPa to 5,000kPa, from 1000 kPa to 4,500kPa, from 1000 kPa to 4,0500kPa. from 1000 kPa to 3,500kPa, from 1000 kPa to 3,000 kPa, from 1000 kPa to 2,500kPa or from 1000 kPa to 2,000kPa.

[0115] In embodiments, the supported bis(phenoxy-phenyl) catalyst of the present disclosure may be utilized to polymerize a single type of olefin, producing a homopolymer. However, additional a-olefins may be incorporated into the polymerization scheme in other embodiments. The additional a-olefin comonomers typically have no more than 20 carbon atoms. For example, the catalyst systems of the present disclosure may polymerize ethylene and, optionally, one or more (C3-C12)a-olefin comonomers in a slurry-phase reactor to produce a polyethylene or a polyethylene copolymer resin. Exemplary (C3-C12)a-olefin comonomers include, but are not limited to, propylene, 1 -butene, 1 -pentene, 1 -hexene, 1 -heptene, 1 -octene, 1 -nonene, 1 -decene, and 4-methyl-l-pentene. For example, the one or more (C3-C12)a-olefin comonomers may be selected from the group consisting of propylene, 1 -butene, 1 -hexene, and 1 -octene; or, in the alternative, from the group consisting of 1 -hexene and 1 -octene.

[0116] In embodiments, the one or more (C3-C12)a-olefin comonomers, when used, may not be derived from propylene. That is, the one or more (C3-C12)a-olefin comonomers may be substantially free of propylene. The term "substantially free" of a compound means the material or mixture includes less than 1.0 wt.% of the compound. For example, the one or more (C3-C12)a-olefin comonomers, which may be substantially free of propylene, may include less than 1.0 wt.% propylene, such as less than 0.8 wt.% propylene, less than 0.6 wt.% propylene, less than 0.4 wt.% propylene, or less than 0.2 wt.% propylene.

[0117] In embodiments, the polyethylene produced, for example homopolymers and / or interpolymers (including copolymers) of ethylene and. optionally, one or more comonomers may include at least 50 mole percent (mol.%) monomer units derived from ethylene.

[0118] For example, the polyethylene may include at least 60 mol.%, at least 70 mol.%, at least 80 mol.%, or at least 90 mol.% monomer units derived from ethylene. In embodiments, the polyethylene includes from 50 mol.% to 100 mol.% monomer units derived from ethylene. For example, the polyethylene may include from 50 mol.% to 90 mol.%, from 50 mol.% to 80 mol.%, from 50 mol.% to 70 mol.%, from 50 mol.% to 60 mol.%, from 60 mol.% to 100 mol.%, from 60 mol.% to 90 mol.%, from 60 mol.% to 80 mol.%, from 60 mol.% to 70 mol.%, from 70 mol.% to 100 mol.%, from 70 mol.% to 90 mol.%, from 70 mol.% to 80 mol.%, from 80 mol.% to 100 mol.%, from 80 mol.% to 90 mol.%, or from 90 mol.% to 100 mol.% monomer units derived from ethylene.

[0119] In embodiments, the polyethylene produced includes at least 90 mol.% monomer units derived from ethylene. For example, the polyethylene may include at least 93 mol.%, at least 96 mol.%, at least 97 mol.%, or at least 99 mol.% monomer units derived from ethylene. In embodiments, the polyethylene includes from 90 mol.% to 100 mol.% monomer units derived from ethylene. For example, the polyethylene may include from 90 mol.% to 99.5 mol.%, from 90 mol.% to 99 mol.%, from 90 mol.% to 97 mol.%, from 90 mol.% to 96 mol.%, from 90 mol.% to 93 mol.%, from 93 mol.% to 100 mol.%, from 93 mol.% to 99.5 mol.%, from 93 mol.% to 99 mol.%, from 93 mol.% to 97 mol.%, from 93 mol.% to 96 mol.%, from 96 mol.% to 100 mol.%, from 96 mol.% to 99.5 mol.%, from 96 mol.% to 99 mol.%, from 96 mol.% to 97 mol.%, from 97 mol.% to 100 mol.%, from 97 mol.% to 99.5 mol.%, from 97 mol.% to 99 mol.%, from 99 mol.% to 100 mol.%, from 99 mol.% to 99.5 mol.%, or from 99.5 mol.% to 100 mol.% monomer units derived from ethylene.

[0120] In embodiments, the polyethylene copolymer resin produced includes less than 50 mol.% monomer units derived from one or more (C3-C12)a-olefin comonomers. For example, the polyethylene copolymer resin may include less than 40 mol.%, less than 30 mol.%, less than 20 mol.% or less than 10 mol.% monomer units derived from one or more (C3-C12)a-olefin comonomers. In embodiments, the polyethylene copolymer resin includes from greater than 0 mol.% to 50 mol.% monomer units derived from one or more (C3-C12)a-olefin comonomers. For example, the polyethylene copolymer resin may include from greater than 0 mol.% to 40 mol.%, from greater than 0 mol.% to 30 mol.%, from greater than 0 mol.% to 20 mol.%, from greater than 0 mol.% to 10 mol.%, from greater than 0 mol.% to 5 mol.%, from greater than 0 mol.% to 1 mol.%, from 1 mol.% to 50 mol.%, from 1 mol.% to 40 mol.%. from 1 mol.% to 30 mol.%, from 1 mol.% to 20 mol.%, from 1 mol.% to 10 mol.%, from 1 mol.% to 5 mol.%, from 5 mol.% to 50 mol.%, from 5 mol.% to 40 mol.%, from 5 mol.% to 30 mol.%, from 5 mol.% to 20 mol.%, from mol.% to 10 mol.%, from 10 mol.% to 50 mol.%, from 10 mol.% to 40 mol.%, from 10 mol.% to 30 mol.%, from 10 mol.% to 20 mol.%, from 20 mol.% to 50 mol.%, from 20 mol.% to 40 mol.%, from 20 mol.% to 30 mol.%, from 30 mol.% to 50 mol.%, from 30 mol.% to 40 mol.%, or from 40 mol.% to 50 mol.% monomer units derived from one or more (C3-C12)a-olefin comonomers.

[0121] In some embodiments, the supported bis(phenoxy-phenyl) catalyst of the present disclosure does not include additives. An additive is a chemical agent present during the polymerization reaction the does not deter olefin propagation. In one or more embodiments, the supported bis(phenoxy-phenyl) catalyst can include an additive. In some embodiments, the additives function as a co-catalyst. In other embodiments, the additives function as a scavenger or scavenging agent. A co-catalyst is a reagent that reacts in cooperation with a catalyst to catalyze the reaction or improve the catalytic activity of the supported bis(phenoxy-phenyl) catalyst. A scavenging agent sequesters impurities in the reactor prior to addition of the precatalyst, and as such, does not constitute and activator. Lower loading of alumoxanes do not act as co-catalysts, rather they serve as scavenging agent. Suitable additives may include, but are not limited to, alkylaluminum; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). Combinations of one or more of the foregoing additives and techniques are also contemplated. The term “alkyl aluminum” means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, a modified methylaluminoxane and isobutylalumoxane.

[0122] In some embodiments, the additive is a Lewis acid Group 13 metal compounds containing (Ci-C2o)hydrocarbyl substituents as described herein. In some embodiments, the additives include tri((Ci-C2o)hydrocarbyl)-substituted-aluminum or tri((Ci-C2o)hydrocarbyl)-boron compounds. In other embodiments, the additives are chosen from tri(hydrocarbyl)-substituted-aluminum, tri((C l-C20)hydrocarbyl)-boron compounds,

[0123] tri((Cl-C10)alkyl)aluminum, tri((C6-Ci8)aryl)boron compounds, and halogenated (including perhalogenated) derivatives thereof.

[0124] In one or more embodiments, the polymerization process further includes a borate- based additive. In some embodiments, the borate-based additive is selected from tris(fluoro- substituted phenyl)boranes, tris(pentafluorophenyl)borane. In some embodiments, the co-catalyst is a tri((C 1-C20)hydrocarbyl)ammonium tetra((C 1-C20)hydrocarbyl)borate (e.g. bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate). As used herein, the term “ammonium” means a nitrogen cation that is a ((Ci-C2o)hydrocarbyl)4N+a

[0125] ((Cl-C20)hydrocarbyl)3N(H)+, a ((Cl-C20)hydrocarbyl)2N(H)2+,

[0126] (Cl-C20)hydrocarbylN(H)3+, or N(H)4+, wherein each (Cl-C20)hydrocarbyl, when two or more are present, may be the same or different.

[0127] In one or more embodiments, the additive may be chosen from polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as inert, compatible, noncoordinating, ion forming compounds. Exemplary suitable additives include, but are not limited to modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(l-)ammonium, triethyl aluminum, butylatedhydroxy-toluene diethyl aluminum, bis-(butylatedhydroxy-toluene) ethyl aluminum, tris-(butylatedhydroxy-toluene) aluminum and combinations thereof.

[0128] In some embodiments, one or more co-catalysts may be used in combination with each other. A specific example of a co-catalyst combination is a mixture of a

[0129] tri((Ci-Cs)hydrocarbyl)aluminum, tri((Ci-C4)hydrocarbyl)borane, tri((C6-Cis)aryl)borane or an ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of total number of moles of one or more metal-ligand complexes of formula (I) to total number of moles of one or more of the co-catalysts is from 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments, at least 1:1000; and 10:1 or less, and in some other embodiments, 1:1 or less. When an alumoxane alone is used as the co-catalyst, preferably the ratio Al of the alumoxane and metal of the metal ligand complex of formula (I) (Al / M) is at least 20. When tris(pentafluorophenyl)borane alone is used as the co-catalyst, in some other embodiments, the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of one or more metal-ligand complexes of formula (I) from 0.5: 1 to 10:1. from 1:1 to 6:1, or from 1:1 to 5:1.

[0130] The slurry-phase reactor system of the present disclosure may further include one or more additives such as a chain transfer agent or a promoter. The chain transfer agents are known and may be alkyl metal such as diethyl zinc. Promoters are known such as in US 4,988,783 and may include chloroform, CFCI3, trichloroethane, and difluoro tetrachloroethane. Prior to reactor start up, a scavenging agent may be used to react with moisture and during reactor transitions a scavenging agent may be used to react with excess activator. Scavenging agents may be a trialkylaluminum. The slurry-phase reactor system of the present disclosure may be operated free of (not deliberately added) scavenging agents. The slurry-phase reactor system of the present disclosure may further include an amount (e.g., 0.5 to 200 ppm based on all feeds into reactor) of one or more static control agents and / or one or more continuity additives such as aluminum stearate or polyethyleneimine. The static control agent(s) may be added to the slurry-phase reactor to inhibit formation or buildup of static charge therein.

[0131] The slurry-phase reactor system of the present disclosure may be a commercial scale slurry-phase reactor systems such as the UNIPOL™ PE Process reactor, which are available from Univation Technologies, LLC, a subsidiary of The Dow Chemical Company, Midland, Michigan, USA. With consideration to the discussion herein, the following aspect of the present disclosure are provided:

[0132] Aspect 1 provides a supported bis (phenoxy-phenyl) catalyst, comprising: a compound of Formula (I):

[0133]

[0134] where: M is Sc, Y, or a lanthanide metal; X is a ligand chosen from (Ci-C4o)hydrocarbyl.

[0135] (Ci-C4o)heterohydrocarbyl, -CH2S1(RC)3-Q(ORC)Q, -S1(RC)3-Q(ORC)Q, -OS1(RC)3-Q(ORC)Q, -CH2Ge(Rc)3-Q(ORc)Q, -Ge(Rc)3-Q(ORc)Q, -P(Rc)2-w(ORc)w, -P(O)(Rc)2.w(ORc)w, -N(RC)2, -NH(RC), -N(Si(Rc) )2, -NRcSi(Rc)3, -NHSi(Rc)3, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC, -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=CH(RC), -N=CH2, -N=P(RC)3, -OC(O)RC, -C(O)ORc, -N(Rc)C(O)Rc, -N(Rc)C(O)H. -NHC(O)Rc, -C(O)N(Rc)2. -C(O)NHRc, -C(O)NH2, a halogen, B(RY)4, A1(RY)4, or Ga(RY)4, or a hydrogen, wherein each Rcis independently a substituted or unsubstituted (Ci-C3o)hydrocarbyl, or a substituted or unsubstituted (Ci-C3o)heterohydrocarbyl, and each Q is 0, 1, 2 or 3. and each W is 0, 1, or 2; each RYis -H, (Ci-C3o)hydrocarbyl, or halogen atom; each T is independently a Lewis Base; n is 0, 1, or 2, when n is 1, X and T are optionally linked, when n is 2, X and one of T are optionally linked; the metal-ligand complex is overall charge-neutral: each Z is independently chosen from -O-, -S-, -N(RN)-, or -P(Rp)-, wherein the dotted line optionally defines a dative bond; R1and R16are independently selected from the group consisting of (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, -N=C(RC)2, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-, or halogen; R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15are independently selected from -H, (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(RP)2, -N(RN)2-ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, (Rc)2C=N- (RC)2P=N- RCC(O)O- RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)- and halogen; L is

[0136] (Ci-C4o)hydrocarbylene or (Ci-C4o)heterohydrocarbylene; and each Rc, Rp, and RNin formula (I) is independently a (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl. or -H; an inert support, wherein the compound of Formula (I) is supported on the inert support.

[0137] Aspect 2 provides the supported bis(phenoxy-phenyl) catalyst of aspect 1, where R1and R16are chosen from radicals having Formula (II) and radicals having Formula (III):

[0138]

[0139] where each of R17–24, and R25–33is independently chosen from -H, (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3. RCS(O)-, RCS(O)2- (RC)2C=N- RCC(O)O- RCOC(O)-, RCC(O)N(RN)-, (RC)2NC(O)-or halogen.

[0140] Aspect 3 provides the supported bis(phenoxy-phenyl) catalyst according to aspect 2, wherein R18and R23are (Ci-C2o)hydrocarbyl, -Si[(Ci-C2o)hydrocarbyl]3, or -Ge[(Ci-C2o)hydrocarbyl]3.

[0141] Aspect 4 provides the supported bis(phenoxy-phenyl) catalyst according to aspect 2, wherein R19and R22are (Ci-C2o)hydrocarbyl, -Si[(Ci-C2o)hydrocarbyl]3, or -Ge[(Ci-C2o)hydrocarbyl]3.

[0142] Aspect 5 provides the supported bis(phenoxy-phenyl) catalyst according to any one of aspects 2 to 4, wherein R17, R20, R21and R24are -H.

[0143] Aspect 6 provides the supported bis(phenoxy-phenyl) catalyst according to aspect 2, wherein R26and R33are (Ci-C2o)hydrocarbyl. -Si[(Ci-C2o)hydrocarbyl]3, or -Ge[(Ci-C2o)hydrocarbyl]3.

[0144] Aspect 7 provides the supported bis(phenoxy-phenyl) catalyst according to aspect 2, wherein R27and R31are (Ci-C2o)hydrocarbyl, -Si[(Ci-C2o)hydrocarbyl]3, or -Ge[(Ci-C2o)hydrocarbyl]3.

[0145] Aspect 8 provides the supported bis(phenoxy-phenyl) catalyst according to any one of aspects 6 to 7, wherein R25, R28, R29, R30and R33are -H. Aspect 9 provides the supported bis(phenoxy-phenyl) catalyst according to any one of aspects 1 to 8, wherein at least one of R8and R9is not -H.

[0146] Aspect 10 provides the supported bis(phenoxy-phenyl) catalyst according to any one of aspects 1 to 9, wherein R8and R9are (Ci-C5)hydrocarbyl.

[0147] Aspect 11 provides the supported bis(phenoxy-phenyl) catalyst according to any one of aspects 1 to 10, wherein R6and R11are halogen.

[0148] Aspect 12 provides the supported bis (phenoxy-phenyl) catalyst according to any one of aspects 1 to 11, wherein R3and R14are (Ci-C5)hydrocarbyl.

[0149] Aspect 13 provides the supported bis(phenoxy-phenyl) catalyst according to any one of aspects 1 to 12, where L is selected from the group of –CH2–, –CH2(CH2)mCH2– where m is from 0 to 3, –CH2Si(RC)2CH2–, –CH2Ge(RC)2CH2–, –CH(CH3)CH2C*H (CH3), and –CH2(phen-1,2-di-yl)CH2–, where each Rcin L is (Ci-C2o)hydrocarbyl, and “C*” is a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical.

[0150] Aspect 14 provides the supported bis (phenoxy-phenyl) catalyst according to any one of aspects 1 to 13, wherein X is -CH2Si[(Ci-C2o)alkyl]3, (Ci-Ci2)alkyl, or halogen atom.

[0151] Aspect 15 provides the supported bis (phenoxy-phenyl) catalyst according to any one of aspects 1 to 14, wherein n is 1 or 2; and at least one T is (Ci-C2o)heterohydrocarbon, wherein the hetero atom of the heterohydrocarbon is oxygen.

[0152] Aspect 16 provides the supported bis(phenoxy-phenyl) catalyst according to any one of aspects 1 to 15, wherein n is 1 or 2; and at least one T is tetrahydrofuran, diethyl ether, or methyl tert-butyl ether (MTBE).

[0153] Aspect 17 provides the supported bis(phenoxy-phenyl) catalyst according to any one of aspects 1 to 16, wherein: R2, R4, R5, R7, R10, R12, R13, and R15are hydrogen; and each Z is oxygen.

[0154] Aspect 18 provides the supported bis(phenoxy-phenyl) catalyst according to any one of aspects 1 to 17, wherein the supported bis (phenoxy-phenyl) catalyst further includes an aluminoxane to form the supported bis(phenoxy-phenyl) catalyst.

[0155] Aspect 19 provides the supported bis(phenoxy-phenyl) catalyst according to aspect 18, wherein the aluminoxane is selected from the group consisting of an aluminum alkyl, an aluminoxane compound and a combination thereof. Aspect 20 provides the supported bis(phenoxy-phenyl) catalyst according to aspect 19, wherein the alkyl aluminum and the aluminoxane are selected from the group consisting of methylaluminoxane (MAO), a modified methylaluminoxane (MMAO). trimethylaluminum (TMA), triethylaluminum (TEA), ethylaluminum sesquichloride (EASC) and combinations thereof.

[0156] Aspect 21 provides the supported bis (phenoxy-phenyl) catalyst according to any one of aspects 18 to 20, wherein the aluminoxane is methylaluminoxane (MAO).

[0157] Aspect 22 provides the supported bis (phenoxy-phenyl) catalyst according to any one of aspects 1 to 21, wherein the inert support is selected from the group consisting of silica, fumed silica, alumina, clay, talc and combinations thereof.

[0158] Aspect 23 provides the supported bis (phenoxy-phenyl) catalyst according to any one of aspects 1 to 22, wherein the inert support has a D50 particle size in a range of 8 to 40 microns.

[0159] Aspect 24 provides a polymerization process for forming an ethylene-based polymer comprising: polymerizing ethylene and optionally one or more (C3-C12) a-olefins in a slurryphase polymerization reactor under olefin polymerizing conditions in the presence of a catalyst system comprising a compound of Formula (I) and one or more inert supports, wherein the compound of Formula (I) has the structure:

[0160]

[0161] (I)

[0162] where: M is Sc, Y, or a lanthanide metal; X is a ligand chosen from (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl. -CH2Si(Rc)3-Q(ORc)Q, -SI(RC)3-Q(ORC)Q, -OSi(Rc)3-Q(ORc)Q, -CH2Ge(Rc)3 Q(ORC)Q, -Ge(Rc)3Q(ORc)Q, -P(Rc)2-w(ORc)w, -P(O)(Rc)2-w(ORc)w, -N(RC)2, -NH(RC), -N(Si(Rc)3)2. -NRcSi(Rc)3. -NHSi(Rc)3, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC. -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=CH(RC), -N=CH2, -N=P(RC)3, -OC(O)RC. -C(O)ORc, -N(Rc)C(O)Rc, -N(Rc)C(O)H, -NHC(O)Rc, -C(O)N(Rc)2, -C(O)NHRc, -C(O)NH2, a halogen, B(RY)4, A1(RY)4, or Ga(RY)4, or a hydrogen, wherein each Rcis independently a substituted or unsubstituted (Ci-C3o)hydrocarbyl. or a substituted or unsubstituted (Ci-C3o)heterohydrocarbyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1, or 2; each RYis -H, (Ci-C3o)hydrocarbyl, or halogen atom; each T is independently a Lewis Base; n is 0. 1, or 2, when n is 1, X and T are optionally linked, when n is 2, X and one of T are optionally linked; the metal-ligand complex is overall charge-neutral; each Z is independently chosen from -O-, -S-, -N(RN)-, or -P(Rp)-, wherein the dotted line optionally defines a dative bond; R1and R16are independently selected from the group consisting of (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3. RCS(O)-, RCS(O)2-, -N=C(RC)2, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-. (RC)2NC(O)-, or halogen; R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15are independently selected from -H, (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(RP)2, -N(RN)2-ORC. -SRC. -NO2, -CN. -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-(RC)2P=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-, and halogen; L is

[0163] (Ci-C4o)hydrocarbylene or (Ci-C4o)heterohydrocarbylene; and each Rc, Rp, and RNin formula (I) is independently a (Ci-C3o)hydrocarbyl, (Ci-C3o)heterohydrocarbyl, or -H.

[0164] Aspect 24 provides the polymerization process of aspect 23, wherein the catalyst system further comprises at least one co-catalyst.

[0165] Aspect 25 provides the polymerization process of aspect 24, wherein a co-catalyst is absent from the catalyst system.

[0166] Aspect 26 provides the polymerization process of any one of aspects 23 to 25, wherein the catalyst system further comprises an additive.

[0167] Aspect 27 provides the polymerization process of aspect 26, wherein the additive is methylaluminoxane or a modified methylaluminoxane.

[0168] Aspect 28 provides the polymerization process of aspect 27, wherein the additive is alkylaluminum.

[0169] The procedures for synthesizing the coordination complex of Compounds (I) - (V) of the present disclosure are provided below. Examples (EX) 1 - EX 6 are supported bis(phenoxy- phenyl) catalysts prepared according to the present disclosure and EX 7-EX 22 are polymerization results obtained from EX 1 - EX 6. It is understood that EX 1 - EX 22 are provided to illustrate embodiments described in this disclosure and are not intended to limit the scope of this disclosure or its appended claims.

[0170] All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexanes, tetrahydrofuran, and diethyl ether were purified via passage through activated alumina and, in some cases, Q-5 reactant. Solvents used for experiments performed in a nitrogen-filled glovebox were further dried by storage over activated 4A molecular sieves. Glassware for moisture- sensitive reactions was dried in an oven overnight prior to use. NMR spectra were recorded on Bruker 300 MHz spectrometers.

[0171] Chemical shifts for1H NMR data are reported in ppm downfield from internal tetramethylsilane (TMS, 6 scale) using residual protons in the deuterated solvent as references.13C NMR data are determined with1H decoupling, and the chemical shifts are reported downfield from tetramethylsilane (TMS, 5 scale) in ppm versus the using residual carbons in the deuterated solvent as references.

[0172] Synthesis of Compound (I)

[0173]

[0174] In a glovebox, a 20 mL vial was charged with ScCh (24.8 mg, 0.164 mmol, 1.00 equiv) and 4.5 mL dry THF. The mixture was allowed to stir overnight at ambient temperature. After ~16 hours, the slurry was placed in a glovebox freezer for 1 hour. The vial was then treated with methyl lithium (1.56 M in diethyl ether, 0.320 mL, 0.500 mmol, 3.05 equiv). The mixture became homogeneous within a minute. Less than 2 minutes after addition of methyllithium, the ligand 1 was added (225 mg, 0.164 mmol, 1.00 equiv). The mixture stirred for 14 hours, and solvent was removed by vacuum pump. The residue was mixed with 2: 1 hexane:toluene, and the slurry filtered through a 0.45 um syringe filter. The filtrate was concentrated to a white solid.

[0175] The solid was triturated with hexane. The liquid was decanted and the leftover solid dried.

[0176] 150 mg of a white solid was isolated (61%).

[0177] NMR (400 MHz, CD2Cl2) 5 8.22 (dd, J- 7.7, 0.7 Hz, 1H), 8.17 - 8.11 (m, 2H), 7.97 (dd. J = 7.7, 0.8 Hz. 1H), 7.85 (d, J = 1.0 Hz. 1H), 7.69 - 7.63 (m, 2H), 7.56 (s. 1H), 7.55 - 7.47 (m, 4H), 7.44 -7.39 (m, 3H), 7.39 - 7.33 (m, 5H), 7.29 (dd, J = 7.7, 0.9 Hz, 1H), 7.26 - 7.11 (m, 13H), 7.05 - 6.99 (m, 2H), 6.87 (dd, J= 9.4. 3.2 Hz, 1H), 6.59 (dd, J = 9.5, 3.3 Hz, 1H), 6.51 (dd, J= 8.6, 3.2 Hz, 1H), 6.19 (dd, J= 8.6, 3.2 Hz, 1H), 3.94 (ddd, J= 11.0, 8.0, 1.5 Hz, 1H), 3.76 -3.46 (m, 3H), 2.86 - 2.66 (m, 2H), 2.54 (dt, 7= 8.3, 6.4 Hz, 2H), 2.28 (s, 3H), 2.26 (s, 3H), 1.80 - 1.64 (m, 2H), 1.41 (s, 3H), 0.75 (tdd, 7= 6.3, 5.3, 4.7. 2.4 Hz, 4H), 0.70 (s, 6H), 0.68 (s, 3H), 0.62 (s, 3H), 0.61 (s, 3H), 0.40 - 0.32 (m, 9H), 0.22 (s, 3H), -1.69 (s, 3H).

[0178] 13C NMR (101 MHz, CD2Cl2) 8 161.08, 160.59, 158.65, 158.17, 156.20, 155.67, 149.14, 149.11. 148.67, 148.65. 142.29, 141.31. 140.15, 140.11, 139.12, 139.07, 138.92, 138.51, 136.61, 136.53, 136.30, 136.22, 135.54, 134.88, 134.86, 134.77, 134.48, 134.43, 134.17, 134.15, 134.10, 134.03, 134.02, 131.98, 130.78, 130.35, 129.80, 129.04, 128.97, 128.73, 128.63, 128.00, 127.71, 127.57, 127.54, 127.50, 126.43, 125.06, 124.95, 124.84, 124.68, 124.61, 124.59, 124.33, 123.64, 123.10, 119.90, 119.58, 119.32, 118.98, 118.64, 117.82, 117.60, 117.29, 117.06, 116.52, 116.11, 115.98, 115.88, 115.75, 115.16, 114.93, 77.97, 74.39, 70.79, 30.10, 24.19, 19.89, 19.78, 17.08, 15.13, -2.10, -2.27, -2.32, -2.40, -2.63, -2.66, -2.68, -2.82.

[0179] 19F NMR (376 MHz, CD2Cl2) 8 -118.10 (t, J= 9.3 Hz), -118.37 (t, J= 9.3 Hz).

[0180]

[0181] Aryl dibromide 3 was prepared according to the procedures in W02020047384. Boronic ester 2 was prepared according to the procedures in W02024050359.

[0182] A 100 mL round bottom flask was charged with the aryl dibromide 3 (0.842 g, 1.87 mmol, 1.00 equiv), boronic ester 2 (3.09 g, 4.12 mmol, 2.20 equiv), and Pd(Amphos)C12 (66 mg, 0.094 mmol, 5.0 mol%). The flask was connected to a reflux condenser and was placed under a blanket of nitrogen. Dry, degassed THF (19 mL) was added, followed by an aqueous solution of K3PO4 (2 M in water, 3.74 mL, 7.48 mmol, 4.00 equiv). The mixture was stirred at 70 °C under nitrogen for 48 hours.

[0183] The solution was cooled, and the phases were separated. The aqueous phase was extracted with a few small portions of ethyl acetate. Combined organic fractions were concentrated, and the residue purified by chromatography on silica gel (0 to 10% EtOAc in hexane). 2.25 g of a white solid was isolated.

[0184] The residue was dissolved in 10 mL THF, 5 mL MeOH, and 2.5 mL water. HC1 (3.3 M in ethanol, 0.91 mL) was added, and the mixture was allowed to reflux for 5 hours. The solution was cooled and diluted with brine. The product was extracted with several portions of dichloromethane. Combined organic fractions were concentrated and the residue purified by chromatography on silica gel (0 to 80% dichloromethane in hexane). 1.606 g of a white solid was isolated (63%).

[0185] ’H NMR (400 MHz. CDCl3) 88.11 (d. J = 7.6 Hz, 4H). 7.48 - 7.36 (m, 12H). 7.28 (s, 4H), 7.25 - 7.10 (m, 16H), 6.91 (dd, 7= 8.9, 3.2 Hz, 2H), 6.81 (dd, 7= 8.5, 3.1 Hz, 2H), 6.38 (s, 2H), 3.42 (t, 7 = 6.3 Hz, 4H), 2.28 (s, 6H), 1.89 (s, 6H), 1.48 - 1.42 (m. 2H), 0.57 - 0.36 (m, 24H).13C NMR (101 MHz, CDCl3) 8 160.13, 157.71, 149.99, 149.96, 147.69, 140.88, 138.58. 135.58, 134.20, 133.46, 133.38, 132.35, 132.26, 131.50, 130.53, 129.83, 128.95, 127.66, 126.99, 126.97, 125.46, 125.36, 124.13, 119.92, 117.38, 117.15, 116.27, 116.04, 115.83, 70.85, 30.54, 20.49, 16.36, -2.02, -2.04.

[0186] 19F NMR (376 MHz, CDCl3) 5 -118.28 (t, J = 8.8 Hz).

[0187]

[0188] K.3PO4 was dried for 24 hours in an oven set at 150 °C. An oven-dried 40 mL vial was charged with 2-(2-iodo-4-methyl-phenoxy)tetrahydropyran (4.26 g, 13.4 mmol) and cyclohexyl- [7-[cyclohexyl(dimethyl)silyl]-9H-carbazol-2-yl]-dimethyl-silane (3.00 g, 6.70 mmol) then taken into a glove box. K3PO4 (4.41 g, 20.8 mmol) and the N, N’-DMEDA (0.995 mL, 10.0 mmol) were added followed by a mixture of Cui (0.638 g, 3.35 mmol) in dry degassed toluene (16.8 mL). The reaction was initially yellow. The vial was fitted with a small condenser then warmed in a heating block (118-120 °C external) with stirring (3 rice stir bars). After 18 hours about 85% conversion, but aryl iodide still remained. The temperature was increased to 124-126 °C (external, active reflux) and stirring was continued for 24 hours. After a total of 36 hours there was about 95% conversion.

[0189] The solution had turned yellow, then light brown. The reaction was cooled to room temperature then filtered through a plug of basic aluminum oxide (about 20 grams). The plug was washed with diethyl ether (125 mL). The filtrate was evaporated under reduced pressure to give a yellow oil. The yellow oil was roto-evaporated from CH3CN (3 x 15 mL). MeOH / CH3CN (4:1, 25 mL) was added to the oil, and the mixture was rotated on the roto-evaporated with the bath set at 50 °C. After 30 minutes the flask was removed and the mixture was stirred at room temperature for 30 minutes. The MeOH / CHsCN layer was removed using a pipet leaving behind an oil. Again, MeOH / CHsCN (4:1, 25 mL) was added to the oil, and the mixture was rotated on the roto-evaporator with the bath set at 50 °C. After 30 minutes the flask was removed and the mixture was stirred at room temperature for 30 minutes. The CH3CN layer was decanted leaving behind a sticky solid, which upon drying under vacuum afforded cyclohexyl-[7-[cyclohexyl(dimethyl)silyl]-9-(5-methyl-2-tetrahydropyran-2-yloxy-phenyl)carbazol-2-yl]-dimethyl- silane (2.30 g, 3.60 mmol, yield: 54 %) as an off white solid:

[0190] rH NMR (400 MHz, CDCl3) 58.09 (d, J = 7.7 Hz, 2H), 7.38 - 7.32 (m, 4H), 7.32 - 7.29 (m, 1H), 7.30 - 7.22 (m, 2H), 5.27 - 5.15 (m, 1H), 3.56 (td, J = 11.0, 2.9 Hz, 1H), 3.39 (dt, J = 11.2, 4.0 Hz, 1H), 2.40 (s. 3H), 1.75 - 1.58 (m, 12H), 1.48 - 1.31 (m, 2H), 1.24 - 0.96 (m, 12H), 0.89 - 0.71 (m, 2H), 0.34 - 0.11 (m, 12H).

[0191] siftiMr -za w-

[0192]

[0193] Part 1: Borylation

[0194] A 40 mL vial was charged with cyclohexyl-[7-[cyclohexyl(dimethyl)silyl]-9-(5-methyl-2-tetrahydropyran-2-yloxy-phenyl)carbazol-2-yl]-dimethyl-silane (2.30 g, 3.60 mmol) in dry THF (10 mL) and put under nitrogen. The solution was cooled to -78 °C (dry ice / acetone) then n-BuLi in hexanes (2600 mmol / L, 1.66 mL, 4.33 mmol) was added slowly over 15 minutes. The mixture was stirred at this temperature for 15 minutes then transferred to an ice water bath and stirred at this temperature for 2 hours (solution turned from light yellow to a precipitate forming). After this time, the 2-isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (0.956 mL, 4.69 mmol) was added dropwise. The reaction quickly turned light tan, and the precipitate mostly went into solution. The reaction was stirred while the cold bath expired overnight (14 h). The next day the reaction was quenched with the addition of H2O and sat. aq. NH4Cl (30 mL, 1:1), Et? O (30 mL) was added then the phases were transferred to a separatory funnel and separated. The aqueous phase was further extracted with Et2O (2 x 20 mL) and the combined organic extracts were washed with brine (20 mL), dried (Na2SO4), filtered and the majority of the solvent was removed using a roto-evaporator, leaving behind mostly THF.

[0195] Part 2: THP Removal

[0196] THF (12 mL) and MeOH (12 mL) were added to the flask followed by cone. HC1 (0.05 mL). The near colorless solution was rotated on the roto-evaporator for 1 hour. After this time the solvent was removed using the roto-evaporator. The isolated material was roto-evaporated from CH3CN (2 x 10 mL) then MeOH (2 x 10 mL) which provided a solid. 25 mL of MeOH was added to the solid (about 10 mL per gram), and the mixture was stirred vigorously for 30 minutes to ensure all solid was broken up into a free-flowing suspension. The solid was isolated by filtration, and washed with MeOH (3 x 15 mL), to afford 2-[2,7-bis[cyclohexyl(dimethyl)silyl]carbazol-9-yl]-4-methyl-6-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenol (1.50 g, 2.21 mmol, yield: 61 %) as a white solid:

[0197] 1H NMR (400 MHz, CDCl3) 58.09 (d, J = 7.7 Hz, 2H), 7.96 (s, 1H), 7.60 (d, J = 2.3 Hz, 1H), 7.42 (d, J = 2.3 Hz, 1H), 7.35 (d, J = 7.8 Hz, 2H), 7.32 (s, 2H), 2.37 (s, 3H), 1.67 (d, J = 9.5 Hz, 12H), 1.38 (s, 12H), 1.21 - 1.01 (m, 8H), 0.86 - 0.74 (m, 2H), 0.24 (app d, J = 3.9 Hz, 12H).

[0198] Degassed THF (6.5 mL) and degassed water (2 mL) were added to a 40 mL vial charged with 2- [2, 7-bis [dimethyl (phenyl) silyl] carbazol-9-yl] -4-methyl-6- (4,4,5,5-tetramethyL 1,3,2-dioxaborolan-2-yl)phenol (0.979 g, 1.47 mmol), l-bromo-2-[3-(2-bromo-4-fluoro-6-methyl-phenoxy)propoxy]-5-fluoro-3-methyl-benzene (0.300 g, 0.666 mmol), PdCl(crotyl)Amphos (0.0154 g, 0.0333 mmol), and NaOH (0.133 g, 3.33 mmol). The reaction was warmed to 50-52 °C (external temperature) and maintained at this temperature for 18 h. (The reaction went from pale yellow, to orange / red, back to yellow while warming up to 50 °C). Eventually turned dark. After this time, the reaction was cooled to room temperature. Et2O (20 mL) and sat. aq. NH4Cl (10 mL) were added to the reaction mixture. The biphase was transferred to a separatory funnel, then after the layers settled, the organic phase was removed. The aq. phase was further extracted with Et2O (20 mL). The combined Et2O extracts were dried over sodium sulfate (Na2SO4) filtered through a fritted funnel to provide a pale-yellow solution. The solvent was removed under reduced pressure. The resulting material was roto-evaporated from CH3CN (2 x 5 mL). CH3CN (20 mL) and isopropanol (3 mL) were added to the semisolid, which was subsequently warmed on the roto-evaporator (55 °C) for 15 minutes. The flask was removed and the mostly soluble yellow / orange solution was stirred at room temperature for 1 hour. No solid formed, but an insoluble sticky oil formed. Some product was in the mother liquor, so the sample was placed in a freezer (-20 °C) overnight. The solvent was decanted and the insoluble material was dissolved in pentane, passed through a small plug of basic alumina, washing the plug with pentane (30 mL). The combined pentane layers were concentrated to provide 2-[2,7- bis[cyclohexyl(dimethyl)silyl]carbazol-9-yl]-6-[2-[3-[2-[3-[2,7- bis[cyclohexyl(dimethyl)silyl]carbazol-9-yl]-2-hydroxy-5-methyl-phenyl]-4-fluoro-6-methyl- phenoxy]propoxy]-5-fluoro-3-methyl-phenyl]-4-methyl-phenol (0.650 g, 0.466 mmol, yield: 70 %) as a white solid. This material was used without further purification:

[0199] 19F NMR (376 MHz, CDCl3) 8 -118.81.

[0200]

[0201] A THF (11.5 mL, 0.046 M based upon ScCl₃) suspension of trichloroscandium (0.0806 g, 0.533 mmol) (note: break up chunks of ScCl₃ with a spatula prior to adding THF) was stirred vigorously at room temperature for 20 hours (overnight) (still a cloudy suspension, but no "chunks") then methyllithium (890 mmol / L, 1.60 mL, 1.42 mmol) in Et2O was added to the suspension, which was stirred at room temperature for 20 minutes (turned a little yellow), then the ligand 2-[2,7-bis[cyclohexyl(dimethyl)silyl]carbazol-9-yl]-6-[2-[3-[2-[3-[2,7- bis[cyclohexyl(dimethyl)silyl]carbazol-9-yl]-2-hydroxy-5-methyl-phenyl]-4-fluoro-6-methyl- phenoxy]propoxy]-5-fluoro-3-methyl-phenyl]-4-methyl-phenol (0.620 g, 0.444 mmol) in THF (1.5 mL) was added over 3 minutes (caution: gas evolution). The ligand vial was rinsed with additional THF (1 mL), added to the reaction. The reaction mixture stayed slightly yellow in color. The solution was stirred for 3 hours at room temperature then additional ScCh (10 mg) was added, followed by stirring overnight at room temperature. After this time, the volatiles were removed under reduced pressure. The yellow solid was taken up in pentane (10 mL) then filtered through a plug of CELITE. The plug was washed with pentane (2 x 5 mL). The combined pentane layers were concentrated to dryness to afford the product (610 mg, 0.400 mmol, yield: 90 %) as an off white solid. ’H NMR (400 MHz, C6D6) 58.32 (d, J = 7.7 Hz, 2H), 8.26 (d, J = 7.7 Hz, 1H), 8.17 (s, 1H), 8.10 (d, J = 7.7 Hz, 1H), 7.76 (d, J = 9.1 Hz, 2H), 7.65 (s, 1H), 7.64 - 7.54 (m, 3H), 7.42 (d, J = 7.7 Hz, 1H), 7.33 (d, J = 2.4 Hz, 1H), 7.00 (dd, J = 6.2. 2.4 Hz, 2H), 6.90 (d, J = 2.5 Hz. 1H), 6.80 (ddd, J = 12.8, 9.0, 3.2 Hz, 2H), 6.27 (dd, J = 8.3, 3.1 Hz, 1H), 6.04 (dd, J = 8.4, 3.2 Hz, 1H), 4.09 - 4.00 (m, 1H), 3.69 - 3.60 (m, 1H), 3.34 - 3.24 (m, 1H), 3.24 - 3.20 (m, 1H), 3.20 -3.12 (m, 2H), 3.02 - 2.90 (m. 2H), 2.18 (s. 3H). 2.09 (s, 3H), 1.87 (s, 3H), 1.84 - 1.54 (m, 16H), 1.37 - 1.09 (m, 34H), 1.00 (s, 3H), 0.50 (s, 3H), 0.47 (s, 3H), 0.37 (s, 3H), 0.29 (s, 3H), 0.21 (s, 3H), 0.19 (s, 3H), 0.18 (s, 3H), 0.16 (s, 3H), -1.15 (s, 3H);

[0202] 19F NMR (376 MHz, C6D6) 8 -116.78 (d, J = 80.7 Hz).

[0203] Synthesis of Compound (III)

[0204]

[0205] The ligand was prepared following the procedures cited in WO 2017 / 004462 Al.

[0206] A THF (75 mL, 0.038 M based upon ligand) suspension of trichloroscandium (0.522 g, 3.45 mmol) (note: break up chunks of ScCl₃ with a spatula prior to adding THF) was stirred vigorously at room temperature for 20 hours (overnight) (still a cloudy suspension, but no "chunks") then methyllithium (1550 mmol / L, 5.65 mL, 8.76 mmol) in Et₂O was added to the suspension, which was stirred at room temperature for 20 minutes (turned a little yellow), then the ligand 2-[2,7-bis[diisopropyl(octyl)silyl]carbazol-9-yl]-6-[2-[3-[2-[3-[2,7-bis[diisopropyl(octyl)silyl]carbazol-9-yl]-2-hydroxy-5-methyl-phenyl]-4-fluoro-6-methyl-phenoxy]propoxy]-5-fluoro-3-methyl-phenyl]-4-methyl-phenol (5.00 g, 2.87 mmol) in THF (10 mL) was added over 3 minutes. The ligand vial was rinsed with additional THF (2 mL), added to the reaction. The reaction mixture stayed slightly yellow in color. The solution was stirred for 2 hours at room temperature then the volatiles were removed under reduced pressure. The resulting yellow solid was evaporated from pentane (2 x 10 mL). The yellow solid was taken up in pentane (100 mL) then filtered through a plug of CELITE. The plug was washed with pentane (25 mL). The combined pentane layers were concentrated to dryness to afford compound III (5.00 g. 2.67 mmol, yield: 93 %) as a slightly yellow solid: ’H NMR (400 MHz, C6D6) (Select peaks) 88.30 (d, J = 7.7 Hz, 1H), 8.27 (d, J = 7.8 Hz, 1H), 8.23 (d, J = 7.7 Hz, 1H), 8.17 (s, 1H), 8.08 (d, J = 7.7 Hz, 1H), 7.73 (s, 1H), 7.69 (d, J = 8.7 Hz, 2H), 7.61 (dd, J = 9.9, 7.7 Hz, 2H), 7.56 (d. J = 7.8 Hz, 1H). 7.46 (d, J = 7.7 Hz. 1H), 7.23 (d, J = 2.5 Hz, 1H), 6.98 (d, J = 2.4 Hz, 1H), 6.95 - 6.90 (m, 2H), 6.80 (dt, J = 6.4, 3.4 Hz, 2H), 6.34 (dd, J = 8.2, 3.1 Hz, 1H), 6.17 (dd, J = 8.4, 3.2 Hz, 1H), 4.10 (ddd, J = 9.7, 6.4, 2.7 Hz. 1H), 3.78 (ddd, J = 10.2, 7.0. 2.8 Hz. 1H). 3.29 (ddd. J = 14.9. 7.6, 4.7 Hz. 4H), 3.11 - 2.98 (m, 2H), 2.20 (s, 3H), 2.07 (s, 3H), 1.94 (s, 3H), -1.13 (s, 3H);

[0207] 19F NMR (376 MHz, C6D6) 8 -116.37, -116.82.

[0208] Synthesis of Compound (IV)

[0209]

[0210] Prepared following the procedures cited in WO 2017 / 004462 Al. The ligand 2-[2.7-bis [diisopropyl(octyl)silyl]carbazol-9-yl] -6- [2-[3- [2- [3- [2,7-bis[diisopropyl(octyl)silyl]carbazoL 9-yl]-2-hydroxy-5-methyl-phenyl]-4-fluoro-6-methyl-phenoxy]propoxy]-5-fluoro-3-methyl-phenyl]-4-methyl-phenol (0.300 g, 0.172 mmol) in THF (2 mL) was added to a suspension of trichloroscandium (0.0391 g, 0.258 mmol) and N, N-diethylethanamine (0.240 mL, 1.72 mmol) in THF (6 mL). The reaction mixture was warmed to provide a gentle reflux (72-75 °C external) and stirred at this temperature for 72 hours. The reaction mixture was evaporated to dryness under vacuum and the residue was taken up in pentane (5 mL), which was removed by vacuum (repeated 1 more time). The residue was taken up in CH2C12 ~10 mL. After filtration through CELITE, the filter cake was extracted with CH2C12 (5 mL). The combined CH2C12 extracts were evaporated under vacuum to provide the product (310 mg, yield: 95 %) as an off-white solid.

[0211] NMR (400 MHz, C6D6) (Select peaks of product) 88.30 (dd, J = 7.7, 3.2 Hz, 2H), 8.22 (d, J = 7.7 Hz, 1H), 8.16 (s, 1H), 8.06 (d, J = 7.6 Hz, 1H). 7.70 (s, 1H), 7.66 (s, 1H), 7.63 (d, J = 6.9 Hz, 3H), 7.58 (d, J = 7.7 Hz, 1H), 7.49 (d, J = 7.7 Hz, 1H), 7.21 (d, J = 2.4 Hz, 1H), 6.93 (d, J - 2.4 Hz, 1H), 6.88 (q, J = 4.6 Hz, 2H), 6.75 - 6.69 (m, 2H), 6.30 (dd, J = 8.1, 3.1 Hz, 1H), 6.15 (dd, J = 8.4. 3.1 Hz, 1H), 4.16 (ddd. J = 9.8, 6.8, 2.3 Hz, 1H), 3.76 (ddd. J = 10.6, 8.1, 2.3 Hz, 1 H), 3.47 (ddd, J = 9.6, 6.3, 3.0 Hz, 1 H), 3.42 - 3.28 (m, 3H), 3.10 - 3.02 (m, 2H), 2.17 (s, 3H), 2.03 (s, 3H), 1.98 (s, 3H);

[0212] 19F NMR (376 MHz, C6D6) 8 -115.85. -116.07.

[0213] Synthesis of Compound (V)

[0214]

[0215] In a N2-filled glove box, a 40 mL vial was charged with trichloroyttrium (YCl₃) (0.0187 g, 0.0956 mmol) and 2-[2,7-bis[dimethyl(phenyl)silyl]carbazol-9-yl]-6-[2-[3-[2-[3-[2,7-bis[dimethyl(phenyl)silyl]carbazol-9-yl]-2-hydroxy-5-(l,l,3,3-tetramethylbutyl)phenyl]-4-fhioro-6-methyl-phenoxy]propoxy]-5-fluoro-3-methyl-phenyl]-4-(l, 1,3,3-tetramethylbutyl)phenol (0.125 g, 0.0797 mmol). THF (8 mL) was added to the vial followed by N, N-diethylethanamine (0.111 mL, 0.797 mmol). The reaction mixture was warmed to 50 °C and stirred at this temperature for 7 hours. After this time additional YCl₃ (12 mg) was added then after a total of 18 hours the reaction mixture was evaporated to dryness under vacuum and the residue was taken up in pentane (5 mL), which was removed by vacuum. The residue was taken up in CH2CI2 (10 mL) and filtered through CELITE. The filter cake was further extracted with CH2CI2 (5 mL). The combined CH₂Cl₂ extracts were evaporated under vacuum to provide the product (0.125 g, 0.0709 mmol, yield: 89 %) as an off-white solid:

[0216] ’H NMR (400 MHz. C6D6) 88.29 (dd. J= 15.9, 7.7 Hz, 2H), 8.22 - 8.14 (m. 2H). 8.00 (d, J = 7.7 Hz, 1H), 7.82 (d, J = 9.1 Hz, 2H), 7.70 - 7.48 (m, 14H), 7.38 (d, J = 7.7 Hz, 1H), 7.22 (dd, J = 18.2, 9.8 Hz, 9H), 7.03 (tt, J = 8.7, 4.7 Hz, 3H), 6.87 - 6.78 (m, 1H), 6.14 (d, J = 7.8 Hz, 2H), 3.66 - 3.49 (m, 4H), 3.30 (d, J = 9.2 Hz, 1H), 2.92 - 2.71 (m, 2H), 2.55 (s, 2H), 1.69 - 1.46 (m, 3H), 1.37 (d, J- 5.2 Hz, 4H), 1.25 - 1.12 (m, 13H), 1.04 (s, 3H), 0.78 (d, 7- 2.5 Hz, 21H), O.74- 0.69 (m, 21H), 0.66 (d, J= 11.7 Hz, 5H), 0.57 (s, 3H), 0.45 (d, J= 13.2 Hz. 6H), 0.34 (s, 3H);

[0217] Peak Report 19F NMR (376 MHz, C6D6) 8 -114.59, -115.11. Preparation of Supported Catalysts

[0218] Each of the following supported catalysts, Example 1 (EX 1) - EX 6, were prepared and sprayed in a nitrogen-purged glove box using a Buchi Mini Spray Dryer B-290 with the following parameters to yield EX 1 - EX 6: Set Temperature of 140 °C, Outlet Temperature of 75 °C (min.), Aspirator at 60%, and Pump Speed of 130 rpm. The fumed silica for each EX 1 -EX 6 was Cabosil TS-610 and the MAO was obtained from Grace. The slurried mixture was allowed to stir for 30-60 minutes prior to spray drying. The slurried mixtures used to form the supported scandium catalysts of EX 1 - EX 6 were formed as follows:

[0219] Preparation of EX 1

[0220] In an oven-dried glass bottle, 1.29 g of fumed silica was slurried in 34 g of toluene until well dispersed, then 10.8 g of a 10 % solution by weight of MAO in toluene and Compound (I) (0.069 g) were added.

[0221] Preparation of EX 2

[0222] In an oven-dried glass bottle, 1.20 g of fumed silica was slurried in 35 g of toluene until well dispersed, then 10.7 g of a 10 % solution by weight of MAO in toluene and compound (I) (0.173 g) were added.

[0223] Preparation of EX 3

[0224] In an oven-dried glass bottle, 0.93 g of fumed silica was slurried in 25 g of toluene until well dispersed, then 7.7 g of a 10 % solution by weight of MAO in toluene and compound (II) (0.05 g) were added.

[0225] Preparation of EX 4

[0226] In an oven-dried glass bottle, 0.88 g of fumed silica was slurried in 24 g of toluene until well dispersed, then 7.4 g of a 10 % solution by weight of MAO in toluene and compound (III) (0.06 g) were added.

[0227] Preparation of EX 5

[0228] In an oven-dried glass bottle, 0.88 g of fumed silica was slurried in 24 g of toluene until well dispersed, then 7.3 g of a 10 % solution by weight of MAO in toluene and compound (IV) (0.06 g) were added. Preparation of EX 6

[0229] In an oven-dried glass bottle, 0.90 g of fumed silica was slurried in 24 g of toluene until well dispersed, then 7.4 g of a 10 % solution by weight of MAO in toluene and compound (V) (0.05 g) were added.

[0230] Reactor Test Conditions:

[0231] For each of Conditions A-C, the hexene preload (mL) was 10, the H2 pre-load (L) was 3.83, the ethylene partial pressure was 125 psi and the run time was 1 hour. The reactor temperature was 85 °C for Condition A; 102 °C for Condition B and 110 °C for Condition C.

[0232] Table 1. Semi-Batch Reactor Testing Results

[0233] Catalyst Flow

[0234] Ex. Yield Efficiency T

[0235] Cat. Condition Charge Index,m

[0236] No. (g) (gPE / gSc) (°C)

[0237] (mg) 121

[0238] EX EX 1 A 41.0 4.58 124,555 No Flow 133.36

[0239] 7

[0240] EX EX 1 B 40.5 7.49 205,738 No Flow 131.81

[0241] 8

[0242] EX EX 1 C 39.8 9.43 263,568 No Flow 130.55

[0243] 9

[0244] EX EX 2 A 100.6 6.40 28.470 No Flow 132.42

[0245] 10

[0246] EX EX 2 B 39.5 7.36 82,740 No Flow 131.63

[0247] 11

[0248] EX EX 2 C 39.0 8.98 102,758 No Flow 131.28

[0249] 12

[0250] EX EX 3 A 200.0 6.58 36,884 No Flow 129.55

[0251] 13

[0252] EX EX 3 B 199.1 5.18 29,060 No Flow 128.68

[0253] 14

[0254] EX EX 4 A 10.1 4.00 436,031 No Flow 133.28

[0255] 15

[0256] EX EX 4 B 10.5 2.79 293,991 No Flow 131.59

[0257] 16

[0258] EX EX 4 C 50.0 7.60 167,365 No Flow 130.37

[0259] 17

[0260] EX EX 5 A 201.0 10.19 56,435 No Flow 130.66

[0261] 18

[0262] EX EX 5 B 201.0 12.38 68,607 No Flow 127.25

[0263]

[0264] 19 EX

[0265] EX 6 A 10.4 4.40 237,892 No Flow 133.33

[0266] 20

[0267] EX EX 6 B 10.2 3.60 199,087 No Flow 131.92

[0268] 21

[0269] EX EX 6 C 9.6 5.80 337,997 No Flow 130.17

[0270]

[0271] 22

[0272] Slurry-Phase Batch Reactor Test:

[0273] The spray dried catalysts prepared above were used for ethylene / 1 -hexene copolymerizations conducted in the slurry phase in a 2L semi-batch autoclave polymerization reactor. The individual run conditions and the properties of the polymers produced in these runs are tabulated in Table 1.

[0274] Tested Property Results.

[0275] The slurry phase reactor was a 2L stainless steel autoclave. The reactor was conditioned by heating it to 105 °C and purging with 1 slpm nitrogen for 1 hour. Then, it was cooled to < 35 °C and charged with 1 L of isobutane. Once charged with isobutane, the pitched blade turbine agitator was turned on to 750 rpm. Under high pressure of nitrogen, 5 g of SMAO (supported methylaluminoxane) as a scavenger was charged to the reactor. Then, the volume of 1 -hexene was charged to the reactor using a pneumatic metering pump. The nitrogen used to add the SMAO was removed from the reactor by slowly venting the reactor pressure down to 60 psig. Then, 3.83 L of hydrogen was added to the reactor and the reactor was heated to the desired temperature (85, 105 or 110 °C). Ethylene was added to the reactor to the set-point partial pressure of 125 psi. Catalyst was delivered to the reactor as a slurry or a solid by accurately weighing it in a pressurized cylinder under an inert atmosphere in a drybox and subsequently mounting it on the reactor head and injecting into the reactor using high pressure nitrogen. The reactor pressure set-point was adjusted to the current pressure and ethylene was fed to the reactor to maintain this set-point pressure. After the amount of polymer designated for the run was made, the run was stopped by closing the ethylene supply, venting the reactor, and cooling it to ambient temperature. Then, isobutane was vented, the reactor was opened, and polymer was collected for analysis.

[0276] Melt Index: Melt flow index of polyethylene and copolymers was measured via the rate of extrusion of molten polymers through a die of specified length and diameter, under prescribed conditions of temperature, load, piston position in the barrel and duration. Flow index (I21) was determined according to ASTM D1238 (190 °C, 21.6 kg).

[0277] General procedure for Differential Scanning Calorimetry (DSC) on polymers from slurry-phase batch reactor:

[0278] 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.

Claims

What is claimed is:

1. A supported bis(phenoxy-phenyl) catalyst, comprising:(I)where:M is Sc, Y, or a lanthanide metal;X is a ligand chosen from (Ci-C4o)hydrocarbyl,(Ci-C4o)heterohydrocarbyl, -CH2Si(Rc)3-Q(ORc)Q,-Si(Rc)3-Q(ORc)Q, -OSi(Rc)3-Q(ORc)Q, -CH2Ge(Rc)3. Q(ORc)Q,-Ge(Rc)3-Q(ORc)Q, -P(RC)2-W(ORC)W, -P(O)(RC)2-W(ORC)W, -N(RC)2, -NH(RC), -N(Si(Rc)3)2, -NRcSi(Rc)3, -NHSi(Rc)3, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC. -S(O)2RC. -OS(O)2RC. -N=C(RC)2. -N=CH(RC), -N=CH2, -N=P(RC)3, -OC(O)RC, -C(O)ORC, -N(RC)C(O)RC, -N(RC)C(O)H, -NHC(O)Rc, -C(O)N(RC)2, -C(O)NHRC, -C(O)NH2, a halogen, B(RY)4, A1(RY)4, or Ga(RY)4, or a hydrogen, wherein each Rcis independently a substituted or unsubstituted (Ci-C3o)hydrocarbyl, or a substituted or unsubstituted (Ci-C3o)heterohydrocarbyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1, or 2; each RYis -H, (Ci-C3o)hydrocarbyl, or halogen atom;each T is independently a Lewis Base;n is 0, 1, or 2, when n is 1, X and T are optionally linked, when n is 2, X and one of T are optionally linked;the metal-ligand complex is overall charge-neutral;each Z is independently chosen from -O-, -S-, -N(RN)-, or -P(Rp)-, wherein the dotted line optionally defines a dative bond;R1and R16are independently selected from the group consisting of (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-. RCS(O)2- -N=C(RC)2, RCC(O)O- RCOC(O)- RcC(O)N(R)-, (RC)2NC(O)- or halogen;R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15are independently selected from -H, (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(RP)2, -N(RN)2-ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2- (RC)2C=N- (RC)2P=N- RCC(O)O- RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-, and halogen;L is (Ci-C4o)hydrocarbylene or (Ci-C4o)heterohydrocarbylene; andeach Rc, Rp, and RNin formula (I) is independently a (Ci-C3o)hydrocarbyl,(Ci-C3o)heterohydrocarbyl. or -H;an inert support, wherein the compound of Formula (I) is supported on the inert support.

2. The supported bis (phenoxy-phenyl) catalyst of claim 1, where R1and R16are chosen from radicals having Formula (II) and radicals having Formula (III):Rzo VR27T(III)'A26p25where each of R17–24, and R25–33is independently chosen from -H, (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl. -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(RN)2. -ORC. -SRC, -NO2, -CN. -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(RN)-, (RC)2NC(O)-, or halogen.

3. The supported bis (phenoxy-phenyl) catalyst according to claim 2, wherein R18and R23are (Ci-C2o)hydrocarbyl, -Si[(Ci-C2o)hydrocarbyl]3, or -Ge[(Ci-C2o)hydrocarbyl]3; or wherein R19and R22are (Ci-C2o)hydrocarbyl, -Si[(Ci-C2o)hydrocarbyl]3, or-Ge [ (C 1 -C2o)hydrocarby 1]3.

4. The supported bis(phenoxy-phenyl) catalyst according to claim 2, wherein two or more of R26, R27, R31, and R33are (Ci-C2o)hydrocarbyl, -Si[(Ci-C2o)hydrocarbyl]3, or -Ge[(Ci-C2o)hydrocarbyl]3.

5. The supported bis(phenoxy-phenyl) catalyst according to any one of claims 1-4, wherein R8and R9are (Ci-C5)hydrocarbyl; orwherein R8and R9are methyl.

6. The supported bis(phenoxy-phenyl) catalyst according to any one of claims 1-5, wherein R6and R11are selected from (Ci-C3o)hydrocarbyl, hydrogen, or halogen, orwherein R6and R11are methyl or fluorine.

7. The supported bis(phenoxy-phenyl) catalyst according to any one of claims 1-6, where L is selected from the group of -CH2-. -CH2(CH2)mCH2- where m is from 0 to 3, -CH2Si(Rc)2CH2-, -CH2Ge(Rc)2CH2-, -CH(CH3)CH2C*H (CH3), and -CH2(phen-l,2-di-yl)CH2-, where each Rcin L is (Ci-C2o)hydrocarbyl, and “C*” is a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical.

8. The supported bis(phenoxy-phenyl) catalyst according to any one of claims 1-7, wherein X is -CH2Si[(Ci-C2o)alkyl]3, (Ci-Ci2)alkyl, or halogen atom; orwherein X is methyl or -CH2SiMe3.

9. The supported bis (phenoxy-phenyl) catalyst according to any one of claims 1-8, wherein n is 1 or 2; and at least one T is (Ci-C2o)heterohydrocarbon, wherein the hetero atom of the heterohydrocarbon is oxygen: orwherein n is 1 or 2; and at least one T is tetrahydro furan, diethyl ether, or methyl tertbutyl ether (MTBE).

10. The supported bis(phenoxy-phenyl) catalyst according to any one of claims 1-9, wherein the supported bis (phenoxy-phenyl) catalyst further includes an alkyl aluminum or aluminoxane compound to form the supported bis(phenoxy-phenyl) catalyst.

11. The supported bis(phenoxy-phenyl) catalyst according to any one of claims 1-10, wherein the alkyl aluminum or aluminoxane compound is selected from methyl aluminoxane (MAO) or a modified methyl aluminoxane (MMAO).

12. A polymerization process for forming an ethylene-based polymer comprising:polymerizing ethylene and optionally one or more (C3-C12) a-olefins in a slurry-phase polymerization reactor under olefin polymerizing conditions in the presence of a catalyst system comprising a compound of Formula (I) and one or more inert supports, wherein the compound of Formula (I) has the structure:(I) where: M is Sc, Y, or a lanthanide metal;X is a ligand chosen from (Ci-C4o)hydrocarbyl,(Ci-C4o)heterohydrocarbyl, -CH2Si(Rc)3. Q(ORc)Q, -Si(Rc)3. Q(ORc)Q, -OSi(Rc)3. Q(ORc)Q, -CH2Ge(Rc)3. Q(ORc)Q, -Ge(Rc)3. Q(ORc)Q, -P(Rc)2-w(ORc)w, -P(O)(Rc)2-w(ORc)w, -N(RC)2, -NH(RC), -N(Si(Rc)3)2, -NRcSi(Rc)3, -NHSi(Rc)3, -ORC, -SRC, -NO2, -CN, -CF3, -OCF3, -S(O)RC. -S(O)2RC, -OS(O)2RC, -N=C(RC)2, -N=CH(RC), -N=CH2, -N=P(RC)3, -OC(O)RC, -C(O)ORc, -N(Rc)C(O)Rc, -N(Rc)C(O)H, -NHC(O)Rc, -C(O)N(Rc)2, -C(O)NHRc, -C(O)NH2, a halogen, B(RY)4, A1(RY)4, or Ga(RY)4, or a hydrogen, wherein each Rcis independently a substituted or unsubstituted (Ci-C3o)hydrocarbyl. or a substituted or unsubstituted (Ci-C3o)heterohydrocarbyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1, or 2; each RYis -H, (Ci-C3o)hydrocarbyl, or halogen atom;each T is independently a Lewis Base;n is 0, 1, or 2, when n is 1, X and T are optionally linked, when n is 2, X and one of T are optionally linked;the metal-ligand complex is overall charge-neutral;each Z is independently chosen from -O-, -S-, -N(RN)-, or -P(Rp)-, wherein the dotted line optionally defines a dative bond;R1and R16are independently selected from the group consisting of (Ci-C4o)hydrocarbyl. (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2- -N=C(RC)2, RCC(O)O- RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-, or halogen;R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, and R15are independently selected from -H, (Ci-C4o)hydrocarbyl. (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(RN)2-ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-, (RC)2P=N-RcC(O)O-, RcOC(O)-, RcC(O)N(R)-, (Rc)2NC(O)-, and halogen;L is (Ci-C4o)hydrocarbylene or (Ci-C4o)heterohydrocarbylene; andeach Rc, Rp, and RNin formula (I) is independently a (Ci-C3o)hydrocarbyl,(Ci-C3o)heterohydrocarbyl, or -H.

13. The polymerization process of claim 12, wherein a co-catalyst is absent from the catalyst system.

14. The polymerization process of any one of claims 12-13, wherein the catalyst system further comprises an additive.

15. The polymerization process of claim 14, wherein the additive is methylaluminoxane or a modified methylaluminoxane.

Images