Group iv phosphinimine cyclopentadienyl multi-catalyst systems for making poly(ethylene-co-1-alkene) in a gas-phase polymerization reactor

Abstract

Supported catalyst systems, methods of making the same, and methods of making a poly(ethylene-co-1-alkene) copolymer comprising polymerizing, in a gas-phase polymerization reactor, ethylene monomer and at least one 1-alkene comonomer in the presence of the same. The supported catalyst system comprises a support material, an activator, a phosphinimine procatalyst of formula (I), and a metallocene procatalyst of one of formulas (IIa)–(IIc): (I) (IIa) (IIb) (IIc).

Description

85976-WO-PCT / DOW 85976 WO GROUPIV PHOSPHINIMINECYCLOPENTADIENYLMULTI-CATALYSTSYSTEMSFORMAKINGPOLY(ETHYLENE-CO-1-ALKENE)IN AGAS-PHASEPOLYMERIZATIONREACTORCROSS-REFERENCETORELATEDAPPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 652,883 filed May 29, 2024, the contents of which are incorporated in their entirety herein. TECHNICAL FIELD

[0002] Embodiments of the present disclosure are generally directed to supported catalyst systems for olefin polymerization and, more particularly, to supported multi-catalyst systems including Group IV transition metal catalysts, methods of making the same, and polymerization processes incorporating the same in a gas-phase polymerization reactor. BACKGROUND

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

[0004] Polyethylene and polypropylene are manufactured for a wide variety of articles. The polyethylene and polypropylene polymerization process can be varied in a number of respects to produce a wide variety of resultant polyethylene resins having different physical properties that render the various resins suitable for use in different applications. The ethylene monomers and optionally one or more comonomers are present in liquid diluents (such as solvents), such as an alkane or isoalkane, for example isobutane in a solution polymerization reactor, or are present as gases in a gas-phase polymerization reactor. Hydrogen may also be added to the reactor. The catalyst systems for producing polyethylene may typically comprise a chromium-based catalyst system, a Ziegler–Natta catalyst system, and / or a molecular (either metallocene or non-metallocene molecular) catalyst system. The reactants and the catalyst system are circulated at an elevated polymerization temperature around the reactor, thereby producing polyethylene homopolymer or copolymer. Either periodically or continuously, part of the reaction mixture, including the polyethylene product, together with85976-WO-PCT / DOW 85976 WO unreacted ethylene and one or more optional comonomers, is removed from the reactor. The reaction mixture when removed from the reactor may be processed to remove the polyethylene product from the unreacted reactants, with the unreacted reactants typically being recycled back into the reactor. Alternatively, the reaction mixture may be sent to a second reactor serially connected to the first reactor where a second polyethylene fraction may be produced. SUMMARY

[0005] Despite previous research efforts in developing catalyst systems suitable for olefin polymerization, such as polyethylene or polypropylene polymerization, there is still a need to increase the efficiencies of catalyst systems to reduce their cost-in-use, particularly without compromising other critical properties such as native molecular weight, comonomer incorporation. Supported catalyst systems with advantageous productivity, efficiency, operability, resultant polymer properties relative to commercial incumbents are of great interest to the gas-phase polyethylene industry for their potential to reduce cost-in-use. Specifically, catalysts that produce poly(ethylene-co-1-alkene) copolymers with higher comonomer incorporation compared to current zirconocenes and hafnocenes used in single and / or dual catalyst applications are of particular interest.

[0006] It has now been discovered that supported dual-catalyst systems employing cyclopentadienyl tri-alkyl phosphinimine Group IV complexes in combination with metallocene catalysts exhibit high productivities (> 10,000 grams polymer / gram catalyst- hour), under commercially relevant process conditions, compared to existing gas-phase commercial catalyst benchmarks that are used for linear-low to high density applications (e.g., metallocenes). These supported dual-catalyst systems are also capable of producing poly(ethylene-co-1-alkene) copolymers with a broad range of weight average molecular weights, including those with high molecular weights, broad molecular weight distributions (Mw / Mn > 4.0, Mz / Mw ≥ 3.0), and reverse short chain branching distribution (SCBD) or broad orthogonal composition or comonomer distribution (BOCD), as measured using a molecular weight comonomer distribution index (MWCDI) calculator, where an MWCDI > 0.0 is classified as reverse SCBD.

[0007] Further, based on the observed hexene comonomer consumption, comonomer incorporation (wt% comonomer), and melt temperature of the polymer (Tm), these85976-WO-PCT / DOW 85976 WO dual-catalyst systems are able to produce resins with a range of densities. These features make these catalysts amenable to making broad unimodal, bi- and multi-modal resins with additional degrees of freedom in designs for applications for single and / or multi-reactor processes, which can improve the end resin / product performance. Also, these supported dual-molecular catalyst systems can produce polyethylene resins with fractional melt index (I2 ≤ 0.5 dg / min) at a range of density targets with broad melt flow ratio (I21 / I2 ≥ 25) without long-chain branching (LCB), or a measured LCBf (LCB / 1000 carbons) ≤ 0.01 under process amenable conditions for molecular catalysts in a gas-phase reactor, similar to prototypical conditions used for metallocenes.

[0008] Embodiments of this disclosure include supported catalyst systems, methods of making the same, and methods of making a poly(ethylene-co-1-alkene) copolymer comprising polymerizing, in a gas-phase polymerization reactor, ethylene monomer and at least one 1-alkene comonomer in the presence of the same.

[0009] According to a first aspect of the present disclosure, a supported catalyst system described herein include a support material, an activator, a phosphinimine procatalyst of formula (I), and a metallocene procatalyst of one of formulas (IIa)–(IIc):(I) (IIa) (IIb) (IIc)

[0010] In formulas (I) and (IIa)–(IIc), each M is independently titanium, zirconium, or hafnium; A is (C1–C20)heterohydrocarbylene, (C1–C20)hydrocarbylene, or a group comprising one or more heteroatoms independently selected from –Si(RC)2– and –Ge(RC)2–; each X is a monodentate ligand independently selected from (C1−C20)hydrocarbyl, (C1−C20)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,85976-WO-PCT / DOW 85976 WO −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, halogen, B(RY)4, Al(RY)4, Ga(RY)4, and –H, wherein: each RCis independently (C1−C20)hydrocarbyl, (C1−C20)heterohydrocarbyl, or –H; each Q is 0, 1, 2 or 3; each W is 0, 1, or 2; each RYis independently (C1−C20)hydrocarbyl, halogen, or –H; and optionally, in one or more of formulas (IIa)–(IIc), two X ligands are covalently connected to form a metallacycle ring; R1–3are independently selected from (C1−C10)hydrocarbyl, (C1–C10)heterohydrocarbyl, and –H, with any two of R1–3optionally covalently connected to form a non-aromatic ring; and R4–33are independently selected from (C1–C10)hydrocarbyl, (C1–C10)heterohydrocarbyl, (C6–C20)aryl, (C3–C20)heteroaryl, and –H, wherein: any two of R4–8are optionally covalently connected to form a ring; any two of R9–13are optionally covalently connected to form a ring; any two of R14–18are optionally covalently connected to form a ring; any two of R19–25are optionally covalently connected to form a ring; any two of R26–29are optionally covalently connected to form a ring; and any two of R30–33are optionally covalently connected to form a ring.

[0011] A second aspect includes the first aspect, wherein the support material comprises silica or fumed silica.

[0012] A third aspect includes any one of the first or second aspects, wherein the activator comprises methylalumoxane (MAO).

[0013] A fourth aspect includes any one of the preceding aspects, wherein a molar ratio of metal in the activator to the combined metal in the phosphinimine procatalyst and the metallocene procatalyst is from 0.5:1 to 3,500:1.

[0014] A fifth aspect includes any one of the preceding aspects, wherein each X in one or more of formulas (I) and (IIa)–(IIc) is independently methyl or halogen.

[0015] A sixth aspect includes any one of the preceding aspects, wherein at least one of R1, R2, and R3is (C1–C10)alkyl.

[0016] A seventh aspect includes the sixth aspect, wherein the at least one of R1, R2, and R3is tert-butyl.

[0017] An eighth aspect includes the sixth aspect, wherein the at least one of R1, R2, and R3is a cycloalkyl group.85976-WO-PCT / DOW 85976 WO

[0018] A ninth aspect includes any one of the first through fifth aspects, wherein at least one of R1, R2, and R3is phenyl.

[0019] A tenth aspect includes any one of the preceding aspects, wherein at least one of R4–8is an aryl or heteroaryl group.

[0020] An eleventh aspect includes the tenth aspect, wherein the at least one of R4–8is an aryl group that is substituted with one or more halogens.

[0021] A twelfth aspect includes any one of the tenth or eleventh aspects, wherein the at least one of R4–8is pentafluorophenyl.

[0022] A thirteenth aspect includes any one of the preceding aspects, wherein M in formula (I) is titanium.

[0023] A fourteenth aspect includes any one of the preceding aspects, wherein M in each of formulas (IIa)–(IIc) is zirconium or hafnium.

[0024] A fifteenth aspect includes any one of the preceding aspects, wherein R9–33are independently (C1−C8)alkyl or –H.

[0025] A sixteenth aspect includes any one of the preceding aspects, wherein: one of R9–13is (C1–C8)alkyl and the remaining R9–13are –H; and one of R14–18is (C1–C8)alkyl and the remaining R14–18are –H.

[0026] A seventeenth aspect includes any one of the first through fifteenth aspects, wherein: one of R9–13is (C1–C8)alkyl and the remaining R9–13are –H; and two of R19–25are independently (C1–C8)alkyl and the remaining R19–25are –H.

[0027] An eighteenth aspect includes any one of the preceding aspects, wherein: one of R26–29is (C1–C8)alkyl and the remaining R26–29are –H; and one of R30–33is (C1–C8)alkyl and the remaining R30–33are –H.

[0028] A nineteenth aspect includes any one of the preceding aspects, wherein A is the group comprising one or more heteroatoms independently selected from –Si(RC)2– and – Ge(RC)2–.

[0029] A twentieth aspect includes any one of the preceding aspects, wherein A comprises germanium.

[0030] According to a twenty-first aspect of the present disclosure, a method of making the supported catalyst system of any one of the first through twentieth aspects comprises85976-WO-PCT / DOW 85976 WO spray-drying a mixture comprising an inert hydrocarbon solvent, the support material, the activator, the phosphinimine procatalyst, and the metallocene procatalyst.

[0031] According to a twenty-second aspect of the present disclosure, a method of making the supported catalyst system of any one of the first through twentieth aspects comprises: spray-drying a mixture comprising an inert hydrocarbon liquid, a support material, and an activator, thereby forming a spray-dried supported activator; and contacting the spray-dried supported activator with a second inert hydrocarbon liquid, the phosphinimine procatalyst of any one of the first through twentieth aspects, and the metallocene procatalyst of any one of the first through twentieth aspects.

[0032] According to a twenty-third aspect of the present disclosure, a method of making the supported catalyst system of any one of the first through twentieth aspects comprises: preparing a dried supported activator by: spray-drying a mixture comprising an inert hydrocarbon liquid, a support material, and an activator; or conventionally drying the mixture comprising the inert hydrocarbon liquid, the support material, and the activator; preparing a first trim solution comprising an inert hydrocarbon liquid and the phosphinimine procatalyst of any one of the first through twentieth aspects; preparing a second trim solution comprising an inert hydrocarbon liquid and the metallocene procatalyst of any one of the first through twentieth aspects; and contacting the dried supported activator in an inert hydrocarbon liquid with the first trim solution and the second trim solution.

[0033] According to a twenty-fourth aspect of the present disclosure, a method of making the supported catalyst system of any one of the first through twentieth aspects comprises: preparing a supported activator slurry by: adding the activator to an inert hydrocarbon liquid containing the support material; or adding the support material to an inert hydrocarbon liquid containing the activator; and adding the phosphinimine and metallocene procatalysts of any one of the first through twentieth aspects to the supported activator slurry.

[0034] According to a twenty-fifth aspect of the present disclosure, a method of making the supported catalyst system of any one of the first through twentieth aspects comprises: preparing a supported activator slurry by: adding the activator to an inert hydrocarbon liquid containing the support material; or adding the support material to an inert hydrocarbon liquid containing the activator; then adding the phosphinimine procatalyst of any one of the first through twentieth aspects to the supported activator slurry to make a supported85976-WO-PCT / DOW 85976 WO phosphinimine catalyst system; and then adding the metallocene procatalyst of any one of the first through twentieth aspects to supported phosphinimine catalyst system to make the supported catalyst system.

[0035] According to a twenty-sixth aspect of the present disclosure, a method of making the supported catalyst system of any one of the first through twentieth aspects comprises: preparing a supported activator slurry by: adding the activator to an inert hydrocarbon liquid containing the support material; or adding the support material to an inert hydrocarbon liquid containing the activator; then adding the metallocene procatalyst of any one of the first through twentieth aspects to the supported activator slurry to make a supported metallocene catalyst system; and then adding the phosphinimine procatalyst of any one of the first through twentieth aspects to make the supported catalyst system.

[0036] According to a twenty-seventh aspect of the present disclosure, a method of making dried supported catalyst system comprises drying the supported catalyst system of any one of twenty-fourth through twenty-sixth aspects.

[0037] According to a twenty-eighth aspect of the present disclosure, a method of making the supported catalyst system of any one of the first through twentieth aspects comprises: preparing a supported phosphinimine catalyst system by: spray-drying a mixture comprising an inert hydrocarbon liquid, a support material, an activator, and the phosphinimine procatalyst of any one of the first through twentieth aspects; or conventionally drying the mixture comprising the inert hydrocarbon liquid, the support material, the activator and the phosphinimine procatalyst of any one of the first through twentieth aspects; preparing a trim solution comprising an inert hydrocarbon liquid and the metallocene procatalyst of any one of the first through twentieth aspects; and contacting the supported phosphinimine catalyst system with the trim solution of the metallocene procatalyst.

[0038] According to a twenty-ninth aspect of the present disclosure, a method of making the supported catalyst system of any one of the first through twentieth aspects comprises: preparing a supported metallocene catalyst system by: spray-drying a mixture comprising an inert hydrocarbon liquid, a support material, an activator, and the metallocene procatalyst of any one of the first through twentieth aspects; or conventionally drying the mixture comprising the inert hydrocarbon liquid, the support material, the activator and the metallocene procatalyst of any one of the first through twentieth aspects; preparing a trim85976-WO-PCT / DOW 85976 WO solution comprising an inert hydrocarbon solvent and the phosphinimine procatalyst of any one of the first through twentieth aspects; and contacting the supported metallocene catalyst system with the trim solution of the phosphinimine procatalyst.

[0039] According to a thirtieth aspect of the present disclosure, a method of making a poly(ethylene-co-1-alkene) copolymer comprises polymerizing, via gas-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of the catalyst system of any one of the first through twenty-ninth aspects.

[0040] According to a thirty-first aspect of the present disclosure, a method of making a poly(ethylene-co-1-alkene) copolymer comprises polymerizing, in a gas-phase polymerization reactor, ethylene monomer and at least one 1-alkene comonomer in the presence of the supported catalyst system of any one of the twenty-second through twenty- ninth aspects, wherein the supported catalyst system is fed to the gas-phase polymerization reactor without an additional drying step.

[0041] According to a thirty-second aspect of the present disclosure, a method of making a poly(ethylene-co-1-alkene) copolymer comprises polymerizing, via gas-phase polymerization, ethylene monomer and at least one 1-alkene comonomer in the presence of the supported catalyst system of the twenty-seventh aspect.

[0042] A thirty-third aspect includes any one of the thirtieth through thirty-second aspects, wherein the polymerizing is performed at polymerization conditions such that the poly(ethylene-co-1-alkene) copolymer comprises: from 50 to 99.9 wt% units derived from ethylene monomer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer; from 1 to 50 wt% units derived from at least one 1-alkene comonomer, based on the total weight of the poly(ethylene-co-1-alkene) copolymer; and from 0.0001 ppm to 10,000 ppm deactivated derivative of the phosphinimine procatalyst, based on the total weight of the poly(ethylene-co-1-alkene) copolymer.

[0043] A thirty-fourth aspect includes the thirty-third aspect, wherein the deactivated derivative of the phosphinimine procatalyst is produced, in part, by subjecting the supported catalyst system to the polymerization conditions.

[0044] A thirty-fifth aspect includes any one of the thirtieth through thirty-fourth aspects, wherein the at least one 1-alkene comonomer comprises 1-butene or 1-hexene.85976-WO-PCT / DOW 85976 WO

[0045] A thirty-sixth aspect of the present disclosure includes the poly(ethylene-co-1- alkene) copolymer produced from the method of any one of the thirtieth through thirty-fifth aspects.

[0046] A thirty-seventh aspect includes the thirty-sixth aspect, wherein the poly(ethylene- co-1-alkene) copolymer comprises a reverse comonomer distribution, broad orthogonal comonomer distribution, or broad orthogonal composition distribution.

[0047] A thirty-eighth aspect includes any one of the thirty-sixth or thirty-seventh aspects, wherein the poly(ethylene-co-1-alkene) copolymer has a molecular weight comonomer distribution index (MWCDI) greater than zero.

[0048] According to a thirty-ninth aspect of the present disclosure, a poly(ethylene-co-1- alkene) copolymer comprises: from 50 to 99.9 wt% units derived from ethylene monomer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer; from 1 to 50 wt% units derived from at least one 1-alkene comonomer, based on the total weight of the poly(ethylene- co-1-alkene) copolymer; from 0.0001 ppm to 10,000 ppm deactivated derivative of the phosphinimine procatalyst of any one of the first through twentieth aspects, based on the total weight of the poly(ethylene-co-1-alkene) copolymer; a weight average molecular weight from 30,000 to 400,000 g / mol; a melt temperature from 70 to 135 °C; a melt index (I2) from 0 to 400 dg / min; a high load melt flow index (I21) from 1 to 2,000 dg / min; a polydispersity index ≥ 3.0; a Mz / Mw ≥ 3.0; and a reverse short chain branching distribution or broad orthogonal composition distribution, as measured by an MWCDI > 0.0.

[0049] According to a fortieth aspect of the present disclosure, a poly(ethylene-co-1-alkene) copolymer comprises: from 50 to 99.9 wt% units derived from ethylene monomer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer; from 1 to 50 wt% units derived from at least one 1-alkene comonomer, based on the total weight of the poly(ethylene-co-1- alkene) copolymer; from 0.0001 ppm to 10,000 ppm deactivated derivative of the phosphinimine procatalyst of any one of the first through twentieth aspects, based on the total weight of the poly(ethylene-co-1-alkene) copolymer; a Mz / Mw ≥ 3.0; and a reverse short chain branching distribution or broad orthogonal composition distribution, as measured by an MWCDI > 0.0.

[0050] A forty-first aspect includes any one of the first through twentieth aspects, wherein the metallocene procatalyst is one of formulas (IIa) or (IIb).85976-WO-PCT / DOW 85976 WO

[0051] According to a forty-second aspect of the present disclosure, a method of making a poly(ethylene-co-1-alkene) copolymer comprises polymerizing, via gas-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of the catalyst system of the forty-first aspect.

[0052] A forty-third aspect includes the forty-second aspect, wherein the supported catalyst system achieves a catalyst productivity of greater than or equal to 10,000 gpoly / gcat·hour.

[0053] A forty-fourth aspect of the present disclosure includes the poly(ethylene-co-1- alkene) copolymer produced from the method of the forty-second or forty-third aspects.

[0054] According to a forty-fifth aspect of the present disclosure, a poly(ethylene-co-1- alkene) copolymer comprises: from 50 to 99.9 wt% units derived from ethylene monomer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer; from 1 to 50 wt% units derived from at least one 1-alkene comonomer, based on the total weight of the poly(ethylene- co-1-alkene) copolymer; from 0.0001 ppm to 10,000 ppm deactivated derivative of the phosphinimine procatalyst of any one of the first through twentieth aspects, based on the total weight of the poly(ethylene-co-1-alkene) copolymer; a weight average molecular weight from 30,000 to 400,000 g / mol; a melt temperature from 70 to 135 °C; a melt index (I2) from 0 to 400 dg / min; a high load melt flow index (I21) from 1 to 2,000 dg / min; a polydispersity index ≥ 3.0; a Mz / Mw ≥ 3.0; and a reverse short chain branching distribution or broad orthogonal composition distribution, as measured by an MWCDI > 0.0.

[0055] According to a forty-sixth aspect of the present disclosure, a poly(ethylene-co-1- alkene) copolymer comprises: from 50 to 99.9 wt% units derived from ethylene monomer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer; from 1 to 50 wt% units derived from at least one 1-alkene comonomer, based on the total weight of the poly(ethylene- co-1-alkene) copolymer; from 0.0001 ppm to 10,000 ppm deactivated derivative of the phosphinimine procatalyst of any one of the first through twentieth aspects, based on the total weight of the poly(ethylene-co-1-alkene) copolymer; a Mz / Mw ≥ 3.0; and a reverse short chain branching distribution or broad orthogonal composition distribution, as measured by an MWCDI > 0.0.

[0056] A forty-seventh aspect includes any one of the forty-second through forty-sixth aspects, wherein the poly(ethylene-co-1-alkene) copolymer comprises a melt index (I2) of less than or equal to 0.5 and a melt flow ratio (MFR; I21 / I2) of greater than or equal to 25.85976-WO-PCT / DOW 85976 WO

[0057] A forty-eighth aspect includes any one of the first through twentieth aspects, wherein the metallocene procatalyst is formula (IIc).

[0058] According to a forty-ninth aspect of the present disclosure, a method of making the supported catalyst system of any one of the first through twentieth aspects comprises: spray drying a mixture comprising an inert hydrocarbon liquid, the support material, the activator, the phosphinimine procatalyst, and the metallocene procatalyst to make a spray-dried supported catalyst; and contacting the spray-dried supported catalyst with additional phosphinimine procatalyst of formula (I) or additional metallocene procatalyst any one of formulas (IIa)–(IIc) to make the supported catalyst system.

[0059] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. DETAILED DESCRIPTION

[0060] Specific embodiments of catalyst systems will now be described. It should be understood that the catalyst systems of this disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure. Rather, embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0061] Common abbreviations are listed below:

[0062] R, Z, M, X and n: as defined above; Me : methyl; Et : ethyl; Ph : phenyl; Ar : aryl; Bn: benzyl; Pr : n-propyl; i-Pr : iso-propyl; t-Bu : tert-butyl; t-Oct : tert-octyl (2,4,4- trimethylpent-2-yl); n-Oct : n-octyl; Ts : toluene sulfonate; THF : tetrahydrofuran; Et2O : diethyl ether; MeOH: methanol; DMA : dimethylacetamide; DME : dimethoxyethane; CH2Cl2 or DCM : dichloromethane; CCl4 : carbon tetrachloride; EtOH : ethanol; CH3CN : acetonitrile; EtOAc : ethyl acetate; C6D6 : deuterated benzene or benzene-d6 : CDCl3 : deuterated chloroform; n-BuLi : n-butyllithium; MeMgBr : methylmagnesium bromide HfCl4 : hafnium(IV) chloride; HfBn4 : hafnium(IV) tetrabenzyl; ZrCl4 : zirconium(IV) chloride; ZrBn4 : zirconium(IV) tetrabenzyl; TiCl4 : titanium(IV) chloride; N2 : nitrogen gas; PhMe: toluene; MAO : methylaluminoxane; MMAO : modified methylaluminoxane; PTFE : polytetrafluoroethylene; GC : gas chromatography; LC : liquid chromatography; NMR :85976-WO-PCT / DOW 85976 WO nuclear magnetic resonance; HRMS: high resolution mass spectrometry; mmol : millimoles; mL : milliliters; M : molar; min: minutes; h : hours; d: days; equiv : equivalents.

[0063] The term “independently selected” is used herein to indicate that the R groups, such as, R1, R2, R3, R4, and R5can 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.). Use of the singular includes use of the plural and vice versa (e.g., a hexane solvent, includes hexanes). A named R group will generally have the structure that is recognized in the art as corresponding to R groups having that name. These definitions are intended to supplement and illustrate, not preclude, the definitions known to those of skill in the art.

[0064] The term “procatalyst” refers to a compound that has catalytic activity when combined with an activator. The term “activator” refers to a compound that chemically reacts with a procatalyst in a manner that converts the procatalyst to a catalytically active catalyst. As used herein, the terms “co-catalyst” and “activator” are interchangeable terms.

[0065] When used to describe certain carbon atom-containing chemical groups, a parenthetical expression having the form “(Cx–Cy)” means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, a (C1–C50)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 version of a chemical group defined using the “(Cx–Cy)” parenthetical may contain more than y carbon atoms depending on the identity of any groups RS. For example, a “(C1–C50)alkyl substituted with exactly one group RS, where RSis phenyl (−C6H5)” may contain from 7 to 56 carbon atoms. Thus, in general when a chemical group defined using the “(Cx–Cy)” parenthetical is substituted by one or more carbon atom-containing substituents RS, the minimum and maximum total number of carbon atoms of the chemical group is determined by adding to both x and y the combined sum of the number of carbon atoms from all of the carbon atom- containing substituents RS.

[0066] In some embodiments, each of the chemical groups (e.g., X, R, Z, etc.) of the metal- ligand complex of formula (I) may be unsubstituted, that is, can be defined without use of a substituent RS, provided the above-mentioned conditions are satisfied. In other embodiments, at least one of the chemical groups of the metal ligand complex of formula (I)85976-WO-PCT / DOW 85976 WO independently contain one or more of the substituents RS. In most embodiments, there are not more than a total of 20 RS, and in other embodiments, not more than a total of 10 RS, and in some embodiments, not more than a total of 5 RSin the metal ligand complex of formula (I). Where the compound contains two or more substituents RS, each RSindependently is bonded to a same or different substituted chemical group. When two or more RSare bonded to a same chemical group, they independently are bonded to a same or different carbon atom or heteroatom in the same chemical group up to and including persubstitution of the chemical group.

[0067] The term “persubstitution” means each 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 each of at least two, but not all, hydrogen atoms bonded to carbon atoms or heteroatoms of a corresponding unsubstituted compound or functional group are replaced by a substituent.

[0068] 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 mean the same thing.

[0069] The term “(C1–C40)hydrocarbyl” means a hydrocarbon radical of from 1 to 40 carbon atoms and the term “(C1–C40)hydrocarbylene” means a hydrocarbon diradical of from 1 to 40 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 (including mono- and poly-cyclic, fused and non-fused polycyclic, including bicyclic; 3 carbon atoms or more) or acyclic, and each hydrocarbon is unsubstituted or substituted by one or more RS.

[0070] In this disclosure, a (C1–C40)hydrocarbyl may be an unsubstituted or substituted (C1–C40)alkyl, (C3–C40)cycloalkyl, (C3–C20)cycloalkyl-(C1–C20)alkylene, (C6–C40)aryl, or (C6–C20)aryl-(C1–C20)alkylene (such as benzyl (−CH2−C6H5)).

[0071] The terms “(C1–C40)alkyl” and “(C1–C18)alkyl” mean a saturated straight or branched hydrocarbon radical of from 1 to 40 carbon atoms or from 1 to 18 carbon atoms, respectively, that is unsubstituted or substituted by one or more RS. Examples of unsubstituted (C1–C40)alkyl are unsubstituted (C1–C20)alkyl; unsubstituted (C1–C10)alkyl; unsubstituted (C1–C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2- methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl.85976-WO-PCT / DOW 85976 WO Examples of substituted (C1–C40)alkyl are substituted (C1–C20)alkyl, substituted (C1– C10)alkyl, trifluoromethyl, and [C45]alkyl. The term “[C45]alkyl” (with square brackets) means there is a maximum of 45 carbon atoms in the radical, including substituents, and is, for example, a (C27–C40)alkyl substituted by one RS, which is a (C1–C5)alkyl, respectively. Each (C1–C5)alkyl independently is methyl, trifluoromethyl, ethyl, 1-propyl, 2-propyl (also called 1-methylethyl and iso-propyl), or 1,1-dimethylethyl (also called tert-butyl).

[0072] The term “(C6–C40)aryl” means an unsubstituted or substituted (by one or more RS) mono-, bi- or tricyclic aromatic hydrocarbon radical of from 6 to 40 carbon atoms, of which at least from 6 to 14 of the carbon atoms are aromatic ring carbon atoms, and the mono-, bi- or tricyclic radical comprises 1, 2 or 3 rings, respectively; wherein the 1 ring is aromatic and the 2 or 3 rings independently are fused or non-fused and at least one of the 2 or 3 rings is aromatic. Examples of unsubstituted (C6–C40)aryl are unsubstituted (C6–C20)aryl unsubstituted (C6–C18)aryl; 2-(C1–C5)alkyl-phenyl; 2,4-bis(C1–C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (C6–C40)aryl are substituted (C1–C20)aryl; substituted (C6–C18)aryl; 2,4-bis[(C20)alkyl]-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-l-yl.

[0073] The term “(C3–C40)cycloalkyl” means a saturated cyclic hydrocarbon radical of from 3 to 40 carbon atoms that is unsubstituted or substituted by one or more RS. Other cycloalkyl groups (e.g., (C3–C12)alkyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more RS. Examples of unsubstituted (C3–C40)cycloalkyl are unsubstituted (C3–C20)cycloalkyl, unsubstituted (C3– C10)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3–C40)cycloalkyl are substituted (C3– C20)cycloalkyl, substituted (C3–C10)cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0074] Examples of (C1–C40)hydrocarbylene include unsubstituted or substituted (C6– C40)arylene, (C3–C40)cycloalkylene, and (C1–C40)alkylene (e.g., (C1–C20)alkylene). In some embodiments, the diradicals are 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., respective 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include α,ω-diradical. The α,ω-diradical is a diradical that has maximum carbon backbone spacing between the radical carbons. Some examples of (C2–C20)alkylene α,ω-diradicals include85976-WO-PCT / DOW 85976 WO ethan-1,2-diyl (i.e. –CH2CH2–), propan-1,3-diyl (i.e. –CH2CH2CH2–), 2-methylpropan-1,3- diyl (i.e. –CH2CH(CH3)CH2–). Some examples of (C6–C50)arylene α,ω-diradicals include phenyl-1,4-diyl, napthalen-2,6-diyl, or napthalen-3,7-diyl.

[0075] The term “(C1–C40)alkylene” means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from 1 to 40 carbon atoms that is unsubstituted or substituted by one or more RS. Examples of unsubstituted (C1–C50)alkylene are unsubstituted (C1–C20)alkylene, including unsubstituted –CH2CH2–, –(CH2)3–, –(CH2)4– , –(CH2)5–, –(CH2)6–, –(CH2)7–, –(CH2)8–, –CH2C*HCH3, and –(CH2)4C*(H)(CH3), in which “C*” denotes a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (C1–C50)alkylene are substituted (C1– C20)alkylene, –CF2–, –C(O)–, and –(CH2)14C(CH3)2(CH2)5– (i.e., a 6,6-dimethyl substituted normal-1,20-eicosylene). Since as mentioned previously two RSmay be taken together to form a (C1–C18)alkylene, examples of substituted (C1–C50)alkylene also include l,2- bis(methylene)cyclopentane, 1,2- bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7- dimethyl-bicyclo[2.2.1]heptane, and 2,3- bis (methylene)bicyclo [2.2.2] octane.

[0076] The term “(C3–C40)cycloalkylene” means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 40 carbon atoms that is unsubstituted or substituted by one or more RS.

[0077] The term “heteroatom” refers to an atom other than hydrogen or carbon. Examples of groups containing one or more than one heteroatoms include O, S, S(O), S(O)2, Si(RC)2, P(RP), N(RN), –N=C(RC)2, –Ge(RC)2–, or –Si(RC)–, where each RCand each RPis independently unsubstituted (C1–C18)hydrocarbyl or –H, and where each RNis unsubstituted (C1–C18)hydrocarbyl.

[0078] The term “heterohydrocarbon” refers to a molecule or molecular framework in which one or more carbon atoms are replaced with a heteroatom.

[0079] The term “(C1–C50)heterohydrocarbyl” means a heterohydrocarbon radical of from 1 to 50 carbon atoms, and the term “(C1–C50)heterohydrocarbylene” means a heterohydrocarbon diradical of from 1 to 50 carbon atoms. The heterohydrocarbon of the (C1–C50)heterohydrocarbyl or the (C1–C50)heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl is on a carbon atom or a heteroatom, and diradicals of the heterohydrocarbyl may be on: (1) one or two carbon atom, (2) one or two85976-WO-PCT / DOW 85976 WO heteroatoms, or (3) a carbon atom and a heteroatom. Each (C1–C50)heterohydrocarbyl and (C1–C50)heterohydrocarbylene may be unsubstituted or substituted (by one or more RS), aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including mono- and poly-cyclic, fused and non-fused polycyclic), or acyclic.

[0080] In some embodiments, the (C1–C40)heterohydrocarbyl independently is unsubstituted or substituted (C1–C40)heteroalkyl, (C1–C40)hydrocarbyl-O–, (C1– C40)hydrocarbyl-S–, (C1–C40)hydrocarbyl-S(O)–, (C1–C40)hydrocarbyl-S(O)2–, (C1– C40)hydrocarbyl-Si(RC)2–, (Cl–C40)hydrocarbyl-N(RN)–, (Cl–C40)hydrocarbyl-P(RP)–, (C2– C40)heterocycloalkyl, (C2–C19)heterocycloalkyl-(C1–C20)alkylene, (C3–C20)cycloalkyl-(C1– C19)heteroalkylene, (C2–C19)heterocycloalkyl-(C1–C20)heteroalkylene, (C1–C40)heteroaryl, (C1–C19)heteroaryl-(C1–C20)alkylene, (C6–C20)aryl-(C1–C19)heteroalkylene, or (C1– C19)heteroaryl-(C1–C20)heteroalkylene.

[0081] The term “heteroaromatic hydrocarbon” means an aromatic hydrocarbon molecule or molecular framework in which one to four carbon atoms are replaced with heteroatoms.

[0082] The term “(C3–C50)heteroaryl” means an unsubstituted or substituted (by one or more RS) mono-, bi- or tricyclic heteroaromatic hydrocarbon radical of from 3 to 50 total carbon atoms, and the mono-, bi- or tricyclic radical comprises 1, 2 or 3 rings, respectively, wherein the 2 or 3 rings independently are fused or non-fused and at least one of the 2 or 3 rings is heteroaromatic. Other heteroaryl groups (e.g., (Cx–Cy)heteroaryl generally, such as (C4–C12)heteroaryl) are defined in an analogous manner as having from x to y carbon atoms (such as 3 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 or 6-membered ring. The 5-membered ring has from 1 to 4 carbon atoms and from 4 to 1 heteroatoms, each heteroatom being O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radical are pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol- 2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 4 or 5 carbon atoms and 2 or 1 heteroatoms, the heteroatoms being N or P. Examples of 6-membered ring heteroaromatic hydrocarbon radical are pyridine-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical can be a fused 5,6- or 6,6- ring system. Examples of the fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radical are indol-1-yl; and benzimidazole-1-yl. Examples of the fused 6,6-ring system85976-WO-PCT / DOW 85976 WO bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical can be a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6- ring system. An example of the fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1- yl. An example of the fused 5,6,6-ring system is 1H-benzo[f] indol-1-yl. An example of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of the fused 6,6,6-ring system is acrydin-9-yl.

[0083] The aforementioned heteroalkyl may be saturated straight or branched chain radicals containing (C1–C50) carbon atoms, or fewer carbon atoms and one or more of the heteroatoms. Likewise, the heteroalkylene may be saturated straight or branched chain diradicals containing from 1 to 50 carbon atoms and one or more than one heteroatoms. The heteroatoms, as defined above, 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 substituted by one or more RS.

[0084] Examples of unsubstituted (C2–C40)heterocycloalkyl are unsubstituted (C2–C20)heterocycloalkyl, unsubstituted (C2–C10)heterocycloalkyl, aziridin-l-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-l-yl, tetrahydrothiophen-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0085] 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−).

[0086] The term “saturated” means lacking carbon–carbon double bonds, carbon–carbon triple bonds, and (in heteroatom-containing groups) carbon–nitrogen, carbon–phosphorous, and carbon–silicon double bonds. Where a saturated chemical group is substituted by one or more substituents RS, one or more double and / or triple bonds optionally may or may not be present in substituents RS. The term “unsaturated” means containing one or more carbon– carbon double bonds, carbon–carbon triple bonds, or (in heteroatom-containing groups) one or more carbon–nitrogen, carbon–phosphorous, or carbon–silicon double bonds, not including any such double bonds that may be present in substituents RS, if any, or in (hetero) aromatic rings, if any.85976-WO-PCT / DOW 85976 WO

[0087] The term “polyethylene” or "ethylene-based polymer" shall mean polymers comprising greater than 50% by weight of units which have been derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of polyethylene known in the art include Low Density Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-site catalyzed Linear Low Density Polyethylene, including both linear and substantially linear low density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).

[0088] Embodiments of the supported catalyst systems described herein include a support material, an activator, a phosphinimine procatalyst of formula (I), and a metallocene procatalyst of one of formulas (IIa)–(IIc):(I) (IIa) (IIb) (IIc)

[0089] In formulas (I) and (IIa)–(IIc), each M is independently titanium, zirconium, or hafnium; A is (C1–C20)heterohydrocarbylene, (C1–C20)hydrocarbylene, or a group comprising one or more heteroatoms independently selected from –Si(RC)2– and –Ge(RC)2–; each X is a monodentate ligand independently selected from (C1−C20)hydrocarbyl, (C1−C20)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, halogen, B(RY)4, Al(RY)4, Ga(RY)4, and –H, wherein: each RCis independently (C1−C20)hydrocarbyl, (C1−C20)heterohydrocarbyl, or –H;85976-WO-PCT / DOW 85976 WO each Q is 0, 1, 2 or 3; each W is 0, 1, or 2; each RYis independently (C1−C20)hydrocarbyl, halogen, or –H; and optionally, in one or more of formulas (IIa)–(IIc), two X ligands are covalently connected to form a metallacycle ring; and R1–3are independently selected from (C1−C10)hydrocarbyl, (C1–C10)heterohydrocarbyl, and –H, with any two of R1–3optionally covalently connected to form a non-aromatic ring; and R4–33are independently selected from (C1–C10)hydrocarbyl, (C1–C10)heterohydrocarbyl, (C6–C20)aryl, (C3–C20)heteroaryl, and –H, wherein: any two of R4–8are optionally covalently connected to form a ring; any two of R9–13are optionally covalently connected to form a ring; any two of R14–18are optionally covalently connected to form a ring; any two of R19–25are optionally covalently connected to form a ring; any two of R26–29are optionally covalently connected to form a ring; and any two of R30–33are optionally covalently connected to form a ring. In embodiments, R9–33are independently (C1−C8)alkyl or –H.

[0090] In embodiments, each X in one or more of formulas (I) and (IIa)–(IIc) is independently methyl or halogen.

[0091] In embodiments, at least one of R1, R2, and R3in formula (I) is (C1–C10)alkyl. In embodiments, at least one of R1, R2, and R3in formula (I) is tert-butyl. In embodiments, at least one of R1, R2, and R3in formula (I) is a cycloalkyl group. In embodiments, at least one of R1, R2, and R3in formula (I) is phenyl.

[0092] In embodiments, at least one of R4–8in formula (I) is an aryl or heteroaryl group. In embodiments, at least one of R4–8in formula (I) is aryl group which that is substituted with one or more halogens. In embodiments, at least one of R4–8in formula (I) is pentafluorophenyl.

[0093] In embodiments, in formula (IIa): one of R9–13is (C1–C8)alkyl and the remaining R9–13are –H; and one of R14–18is (C1–C8)alkyl and the remaining R14–18are –H.

[0094] In embodiments, in formula (IIb): one of R9–13is (C1–C8)alkyl and the remaining R9–13are –H; and two of R19–25are independently (C1–C8)alkyl and the remaining R19–25are –H.

[0095] In embodiments, in formula (IIc): one of R26–29is (C1–C8)alkyl and the remaining R26–29are –H; and one of R30–33is (C1–C8)alkyl and the remaining R30–33are –H.

[0096] In embodiments, M in formula (I) is titanium. In embodiments, M in one or more of formulas (IIa)–(IIb) is zirconium or hafnium. In embodiments, M in each of formulas (IIa)–85976-WO-PCT / DOW 85976 WO (IIc) is zirconium or hafnium. In embodiments, M in each of formulas (IIa)–(IIc) is zirconium. In embodiments, M in each of formulas (IIa)–(IIc) is hafnium.

[0097] In embodiments, A in formula (IIc) is the group comprising one or more heteroatoms independently selected from –Si(RC)2– and –Ge(RC)2–. In embodiments, A comprises germanium.

[0098] In specific embodiments of supported catalyst systems, the phosphinimine procatalyst according to formula (I) may be a metal-ligand complex having the structure of any of Procatalysts MLC-1 to MLC-4:MLC-3 MLC-4

[0099] In specific embodiments of supported catalyst systems, the metallocene procatalyst according one of formulas (IIa)–(IIc) may be a metal-ligand complex having the structure of one of Procatalysts MLC–5 or MLC-6:85976-WO-PCT / DOW 85976 WOMLC-7

[0100] Activator Component

[0101] In embodiments, the procatalysts of formulas (I) and (IIa)–(IIc) may be rendered catalytically active by contacting them to, or combining them with, an activator. A procatalyst that has been rendered catalytically active by contacting it to, or combining it with, an activator may be referred to as a “catalyst system.” That is, as used in the present disclosure, a catalyst system may include a procatalyst and one or more activators. The term “activator” may include any combination of reagents that increases the rate at which a transition metal compound oligomerizes or polymerizes unsaturated monomers, such as olefins. An activator may also affect the molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer. The transition metal compounds may be activated for oligomerization and / or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and or polymerization.85976-WO-PCT / DOW 85976 WO

[0102] Alumoxane activators may be utilized as an activator for one or more of the procatalysts described herein. Alumoxane(s) or aluminoxane(s) are generally oligomeric compounds containing –Al(R)–O– subunits, where R is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide. Mixtures of different alumoxanes and modified alumoxanes may also be used. For further descriptions, see U.S. Patent Nos. 4,665,208; 4,952,540; 5,041,584; 5,091,352; 5,206,199; 5,204,419; 4,874,734; 4,924,018; 4,908,463; 4,968,827; 5,329,032; 5,248,801; 5,235,081; 5,157,137; 5,103,031; and EP 0 561 476; EP 0279 586; EP 0 516 476; EP 0 594 218; and WO 94 / 10180.

[0103] In embodiments, the molar ratio of metal in the activator to metal in the phosphinimine procatalyst, the metallocene procatalyst, or both, is from 0.5:1 to 3,500:1. In embodiments, the molar ratio of metal in the activator to the combined metal in the phosphinimine and metallocene procatalysts is from 0.5:1 to 3,500:1. Suitable activators are commercially available. In some embodiments the aluminum based activator is an alkylaluminum or an alkylaluminoxane (alkylalumoxane). Any alkyl group may be utilized. In some embodiments, each alkyl of the alkylaluminum or alkylaluminoxane is independently (C1–C8)alkyl, (C1–C7)alkyl, (C1–C6)alkyl, or (C1–C4)alkyl.

[0104] Aluminum alkyl or organoaluminum compounds that may be utilized as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n- hexylaluminum, tri-n-octylaluminum and the like.

[0105] Support Component

[0106] In embodiments, the procatalysts described herein, the activator, or both, may be disposed on one or more support materials. For example, the procatalysts may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more support materials. The procatalysts, the activator, or both, may be combined with one or more support materials using one of the support methods well known in the art or as described below. As used in the present disclosure, the procatalysts, the activator, or both, may be in a supported form, for example, when deposited on, contacted with, or incorporated within, adsorbed or absorbed in, or on, one or more support materials.85976-WO-PCT / DOW 85976 WO

[0107] In other embodiments the activator and the support material are contacted together in an inert hydrocarbon liquid to give a suspension of a supported activator in the inert hydrocarbon liquid, then the suspension is contacted with the phosphinimine procatalyst to give a suspension of the supported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed to give the supported catalyst system.

[0108] The removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may include a step of decanting some of the inert hydrocarbon liquid from the suspension. In some embodiments the decanting method comprises pouring off excess inert hydrocarbon liquid from the suspension to give a concentrated suspension of the supported catalyst system.

[0109] The removing of the inert hydrocarbon liquid from the suspension of the supported catalyst system may comprise a step of drying the supported catalyst system. The drying step may comprise a spray-drying method.

[0110] A “support,” which may also be referred to as a “carrier,” refers to any support material, including a porous support material, such as talc, inorganic oxides, and inorganic chlorides. Other support materials include resinous support materials, e.g., polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.

[0111] Suitable support materials, such as inorganic oxides, include oxides of metals of Group 2, 3, 4, 5, 13 or 14 of the IUPAC periodic table. In embodiments, support materials include silica, which may or may not be dehydrated, fumed silica, alumina (e.g., as described in International Patent Application No. 1999 / 060033), silica-alumina, and mixtures of these. The fumed silica may be hydrophilic (untreated), alternatively hydrophobic (treated). In embodiments, the support material is hydrophobic fumed silica, which may be prepared by treating an untreated fumed silica with a treating agent, such as dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane. In some embodiments, support materials include magnesia, titania, zirconia, magnesium chloride (e.g., as described in U.S. Patent No.5,965,477), montmorillonite (e.g., as described in European Patent No.0511665), phyllosilicate, zeolites, talc, clays (e.g., as described in U.S. Patent No. 6,034,187), and mixtures of these. In other embodiments, combinations of these support materials may be85976-WO-PCT / DOW 85976 WO used, such as, for example, silica-chromium, silica-alumina, silica-titania, and combinations of these. Additional support materials may also include those porous acrylic polymers described in European Patent No. 0 767 184. Other support materials may also include nanocomposites described in International Patent Application No. 1999 / 047598; aerogels described in International Patent Application No. 1999 / 048605; spherulites described in U.S. Patent No. 5,972,510; and polymeric beads described in International Patent Application No. 1999 / 050311. An example of a support material is fumed silica available under the trade name CABOSIL TS- 610, or other TS- or TG-series supports, available from Cabot Corporation. Fumed silica is typically a silica with particles 7 to 30 nanometers in size that have been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped.

[0112] In embodiments, the support material is not treated with an electron-withdrawing anion (e.g., fluoride, sulfate, tungstate, Lewis-acidic metal ion, etc.) that has the effect of increasing the Lewis or Bronsted acidity of the support material. Without wishing to be bound by theory, it is believed that increasing the Lewis or Bronsted acidity may increase the rate of deactivation of the catalyst system leading to less total productivity for the catalyst system.

[0113] In embodiments, the support material has a surface area of from 10 square meters per gram (m2 / g) to 700 m2 / g, a pore volume of from 0.1 cubic meters per gram (cm3 / g) to 4.0 cm3 / g, and an average particle size of from 5 microns (µm) to 500 µm. In some embodiments, the support material has a surface area of from 50 m2 / g to 500 m2 / g, a pore volume of from 0.5 cm3 / g to 3.5 cm3 / g, and an average particle size of from 10 µm to 200 µm. In other embodiments, the support material may have a surface area of from 100 m2 / g to 400 m2 / g, a pore volume from 0.8 cm3 / g to 3.0 cm3 / g, and an average particle size of from 5 µm to 100 µm. The average pore size of the support material is typically from 10 Angstroms (Å) to 1,000 Å, such as from 50 Å to 500 Å or from 75 Å to 350 Å.

[0114] The support material may comprise silica, alternatively amorphous silica (not quartz), alternatively a high surface area amorphous silica, e.g., from 500 to 1000 m2 / g. Such silicas are commercially available from several sources including the Davison Chemical Division of W.R. Grace and Company, e.g., Davison 952 and Davison 955 products, and PQ Corporation, e.g., ES70 product. The silica may be in the form of spherical particles, which may be obtained by a spray-drying process. Alternatively, MS3050 product is a silica from85976-WO-PCT / DOW 85976 WO PQ Corporation that is not spray-dried. As procured, these silicas are not calcined (i.e., not dehydrated). Silica that is calcined prior to purchase may also be used as the support material.

[0115] In some embodiments the solid support is a hydrophobic fumed silica. The hydrophobic fumed silica is made by contacting an untreated fumed silica, having surfaces containing silicon-bonded hydroxyl groups (Si-OH groups), with a hydrophobing agent, described later. In some embodiments the hydrophobing agent is a silicon-based hydrophobing agent, containing on average per molecule one or more functional groups reactive with a Si-OH group, to give the hydrophobic fumed silica. The silicon-based hydrophobing agent may be selected from (CH3)2SiCl2, a polydimethylsiloxane, hexamethyldisilazane (HMDZ), and a (C1–C10)alkyl-Si((C1–C10)alkoxy)3 (e.g., an octyltrialkoxysilane such as octyltriethoxysilane, i.e., CH3(CH2)7Si(OCH2CH3)3). In some embodiments the silicon-based hydrophobing agent is dimethyldichlorosilane, i.e., (CH3)2SiCl2. In some embodiments the support material is a dimethyldichlorosilane-treated fumed silica, such as that sold as product TS-610 from Cabot Corporation.

[0116] The support material may be uncalcined or calcined. The calcined support material is made prior to being contacted with a precatalyst, activator, and / or hydrophobing agent, by heating the support material in air to give a calcined support material. The calcining comprises heating the support material at a peak temperature from 350 °C to 850 °C, alternatively from 400 °C to 800 °C, alternatively from 400 °C to 700 °C, alternatively from 500 °C to 650 °C and for a time period from 2 to 24 hours, alternatively from 4 to 16 hours, alternatively from 8 to 12 hours, alternatively from 1 to 4 hours, thereby making the calcined support material. If the support material has not been heated in this way it is an uncalcined support material.

[0117] Methods of Making Supported Catalysts Systems

[0118] Embodiments of the present disclosure also include methods of making supported catalyst systems. In one or more embodiments, methods for producing the supported catalyst system include contacting one or more support materials, one or more activators, and the procatalysts in an inert hydrocarbon liquid to produce the supported catalyst system as a supported dual catalyst system. In some embodiments, the method for producing the catalyst system may include disposing the one or more activators on the one or more support materials to produce a supported activator, and contacting the supported activator with one or more85976-WO-PCT / DOW 85976 WO solutions containing the procatalysts in an inert hydrocarbon liquid (often referred to as a “trim catalyst,” “trim feed,” or “trim solution”).

[0119] For example, in some embodiments, methods for producing the catalyst system include spray-drying a mixture comprising an inert hydrocarbon liquid, a support material, and an activator, thereby forming a spray-dried supported activator, and then contacting the spray-dried supported activator with an inert hydrocarbon liquid containing the phosphinimine procatalyst and the metallocene catalyst. In other embodiments, rather than contacting the spray-dried supported activator with an inert hydrocarbon liquid containing both the phosphinimine procatalyst and the metallocene procatalyst, the method may include preparing a first trim solution comprising an inert hydrocarbon liquid and the phosphinimine procatalyst and a second trim solution comprising an inert hydrocarbon liquid and the metallocene procatalyst, and then contacting the spray-dried supported activator with the first and second trim solutions to produce the supported catalyst system.

[0120] Other methods for producing the catalyst system include conventionally drying a mixture comprising an inert hydrocarbon liquid, a support material, and an activator, thereby forming a dried supported activator, and then contacting the supported activator with an inert hydrocarbon liquid containing the phosphinimine procatalyst and the metallocene catalyst. In embodiments, rather than contacting the dried supported activator with an inert hydrocarbon liquid containing both the phosphinimine procatalyst and the metallocene procatalyst, the method may include preparing a first trim solution comprising an inert hydrocarbon liquid and the phosphinimine procatalyst and a trim solution comprising an inert hydrocarbon liquid and the metallocene procatalyst, and then contacting the supported activator with the first and second trim solutions to produce the supported catalyst system.

[0121] In some embodiments, the method for producing the catalyst system may include mixing one or more support materials, one or more activators, and the procatalysts in an inert hydrocarbon liquid to produce a supported catalyst system. The methods may further include drying the supported catalyst system. More specifically, the methods may include making a mixture of the phosphinimine and metallocene procatalysts, one or more support materials, one or more activators, or a combinations of these, and an inert hydrocarbon liquid. The inert hydrocarbon liquid may then be removed. In embodiments, the removal of the inert hydrocarbon liquid from supported catalyst system may be achieved under reduced pressure (i.e., conventional concentrating method), which yields an evaporated dried supported85976-WO-PCT / DOW 85976 WO catalyst system. In other embodiments, the removing step may be achieved by spray-drying the mixture, which produces spray-dried particles. It should be understood that the drying and / or removing steps may not result in the complete removal of liquids from the resulting catalyst system. That is, the supported catalyst system may include residual amounts (i.e., from 1 wt% to 3 wt%) of the inert hydrocarbon liquid.

[0122] As mentioned, the phosphinimine complexes represented by formula (I) and metallocenes represented by formulas (IIa)-(IIc) can be utilized to make spray-dried catalyst systems, i.e., spray-dried dual catalyst systems. As used herein, “spray-dried” material refers to a material that includes a number of components that have undergone a spray-drying process. Various spray-drying process are known in the art and are suitable for forming the spray-dried catalyst systems disclosed herein.

[0123] In one or more embodiments, the spray-drying process may comprise atomizing a composition including the phosphinimine represented by formula (I) and metallocenes represented by formulas (IIa)-(IIc). A number of other known components may be utilized in the spray-drying process. An atomizer, such as an atomizing nozzle or a centrifugal high speed disc, for example, may be used to create a spray or dispersion of droplets of the composition. The droplets of the composition may then be rapidly dried by contact with an inert drying gas. The inert drying gas may be any gas that is non-reactive under the conditions employed during atomization, such as nitrogen, for example. The inert drying gas may meet the composition at the atomizer, which produces a droplet stream on a continuous basis. Dried particles of the composition may be trapped out of the process in a separator, such as a cyclone, for example, which can separate solids formed from a gaseous mixture of the drying gas, solvent, and other volatile components.

[0124] A spray-dried catalyst system may have the form of a free-flowing powder, for instance. After the spray-drying process, the spray-dried catalyst system and a number of known components may be utilized to form a slurry. The spray-dried catalyst system may be utilized with a diluent to form a slurry suitable for use in olefin polymerization, for example. In one or more embodiments, the slurry may be combined with one or more additional catalysts or other known components prior to delivery into a polymerization reactor.

[0125] In one or more embodiments, the spray-dried catalyst system may be formed by contacting a spray-dried supported activator, such as a spray-dried mixture containing fumed85976-WO-PCT / DOW 85976 WO silica (e.g. Cabosil) and methylaluminoxane (MAO), with a solution containing the phosphinimine procatalyst and a solution containing the metallocene procatalyst. Such solutions containing the phosphinimine and metallocene procatalysts, typically may be made using an inert hydrocarbon liquid, for instance, and are sometimes called trim solutions. In embodiments, the contacting of the spray-dried supported activator with the the trim solution may take place in situ in a feed line heading into a slurry or gas-phase polymerization reactor by contacting the trim solution with a slurry containing the spray-dried supported activator, e.g., mineral oil containing the spray-dried supported activator.

[0126] In some embodiments, methods for producing the spray-dried catalyst system include spray-drying a mixture comprising an inert hydrocarbon liquid, a support material, an activator, and the phosphinimine procatalyst thereby forming a spray-dried supported phosphinine catalyst system, and then contacting that spray-dried supported phosphinimine catalyst with a second inert hydrocarbon liquid containing the metallocene procatalyst. Further embodiments include preparing a trim solution comprising the second inert hydrocarbon liquid and the metallocene procatalyst and then contacting the trim solution with the spray-dried supported phosphinimine catalyst to prepare the spray-dried dual catalyst system. In embodiments wherein a spray-dried supported phosphinimine catalyst is contacted with an inert hydrocarbon liquid and the metallocene procatalyst to make a spray-dried dual catalyst system, the resulting catalyst slurry may be added directly, i.e., without an additional drying step, to a polymerization reactor (e.g., a gas-phase polymerization reactor), or may be dried to produce a dried supported catalyst system which can be added to a polymerization reactor or resuspended in a hydrocarbon liquid and then added to the polymerization reactor.

[0127] As an example, various spray-drying conditions may be utilized for different applications. For instance, the spray-drying process may utilize a drying temperature from 115 °C to 185 °C. Various sizes of orifices of the atomizing nozzle employed during the spray-drying process may be utilized to obtain different particle sizes. Alternatively, for other types of atomizers such as discs, rotational speed, disc size, and the number / size of holes may be adjusted to obtain different particle sizes. One or more embodiments provide that a filler may be utilized in the spray-drying process. Different fillers and amounts thereof may be utilized for various applications.

[0128] In embodiments, methods for making a supported catalyst system may include preparing an initial slurry comprising one or more support materials and / or one or more85976-WO-PCT / DOW 85976 WO activators in an inert hydrocarbon liquid, and then adding additional constituents in various orders to arrive at a suspension containing the one or more support materials, the one or more activators, and the phosphinimine and metallocene procatalysts. For example, in embodiments, the methods may include preparing a supported activator suspension by adding one or more activators to an inert hydrocarbon liquid containing one or more support materials, and then adding the phosphinimine procatalyst and the metallocene procatalyst to the supported activator suspension, wherein the phosphinimine procatalyst and the metallocene procatalyst are added to the supported activator suspension at the same time or at different times, with the phosphinimine procatalyst being added before or after the metallocene procatalyst. In other embodiments, the methods may include preparing a supported activator suspension by adding one or more support materials to an inert hydrocarbon liquid containing one or more activators, and then adding the phosphinimine procatalyst and the metallocene procatalyst to the supported activator suspension, wherein the phosphinimine procatalyst and the metallocene procatalysts are added to the supported activator suspension at the same time or at different times, with the phosphinimine procatalyst being added before or after the metallocene procatalyst.

[0129] In other embodiments of making the supported catalyst systems of the present disclosure, either the phosphinimine catalyst or the metallocene procatalyst is added to an inert hydrocarbon liquid containing one or more support materials or one or more activators, and then the remaining constituents are added in various orders to arrive at a suspension containing the one or more support materials, the one or more activators, and the procatalysts. For example, in embodiments, the methods may include preparing a first procatalyst activator solution by adding the metallocene procatalyst to an inert hydrocarbon liquid containing one or more activators, preparing a second procatalyst solution by adding the phosphinimine procatalyst to the first procatalyst solution, and then adding one or more support materials to the second procatalyst solution to produce the supported catalyst system.

[0130] Further, several of the above-described methods for making supported catalyst systems result in the supported catalyst system being suspended in an inert hydrocarbon liquid. Such supported catalyst systems may be added directly, i.e., without an additional drying step, to a polymerization reactor (e.g., a gas polymerization reactor) or may be conventially-dried or spray-dried to produce a dried supported catalyst system, which can85976-WO-PCT / DOW 85976 WO then be added to a polymerization reactor, or resuspended in an inert hydrocarbon liquid, and then added to a polymerization reactor.

[0131] In further embodiments, methods for making the supported catalyst system may include preparing a supported phosphinimine catalyst by spray-drying or conventionally-drying a mixture containing an inert hydrocarbon liquid, one or more support materials, one or more activators, and the phosphinimine catalyst, and then contacting the supported phosphinimine catalyst with a trim solution comprising an inert hydrocarbon liquid and the metallocene procatalyst to produce the supported catalyst system as a supported dual catalyst system. Alternatively, in embodiments, methods for making the supported catalyst system may include preparing a supported metallocene catalyst by spray-drying or conventionally-drying a mixture containing an inert hydrocarbon liquid one or more support materials, one or more activators, and the metallocene procatalyst, and then contacting the supported metallocene catalyst with a trim solution comprising an inert hydrocarbon liquid and the phosphinimine procatalyst to produce the supported catalyst system as a supported dual catalyst system.

[0132] Polymerization Methods

[0133] As noted above, the supported catalyst systems of the present disclosure may be utilized in processes for producing polymers, such as polyethylene, via the polymerization of olefins, such as ethylene. In embodiments, one or more olefins may be contacted with the supported catalyst systems of the present disclosure in a gas-phase polymerization reactor, such as a gas-phase fluidized bed polymerization reactor. Exemplary gas-phase systems are described in U.S. Patent Nos.5,665,818; 5,677,375; and 6,472,484; and European Patent Nos. 0517868 and 0794200. In embodiments, methods for making a poly(ethylene-co-1-alkene) copolymer include polymerizing, via gas-phase polymerization, ethylene monomer and at least one 1-alkene comonomer in the presence of a supported catalyst system described herein.

[0134] For example, in some embodiments, ethylene monomer and the at least one 1-alkene comonomer may be contacted with a supported catalyst system of the present disclosure in a gas-phase polymerization reactor. The supported catalyst system may be fed to the gas-phase polymerization reactor in neat form (i.e., as a dry solid), as a solution, or as a slurry. For example, in some embodiments, spray-dried particles of the supported catalyst system may85976-WO-PCT / DOW 85976 WO be fed directly to the gas-phase polymerization reactor. In other embodiments, a slurry or suspension of the supported catalyst system in an inert hydrocarbon liquid or mineral oil, may be fed to the reactor.

[0135] In embodiments, the gas-phase polymerization reactor comprises a fluidized bed reactor. A fluidized bed reactor may include a “reaction zone” and a “velocity reduction zone.” The reaction zone may include a bed of growing polymer particles, formed polymer particles, and a minor amount of the spray-dried catalyst system fluidized by the continuous flow of the gaseous monomer and diluent to remove heat of polymerization through the reaction zone. Optionally, some of the re-circulated gases may be cooled and compressed to form liquids that increase the heat removal capacity of the circulating gas stream when readmitted to the reaction zone. A suitable rate of gas flow may be readily determined by simple experiment. Make up of gaseous monomer to the circulating gas stream may be at a rate equal to the rate at which particulate polymer product and monomer associated therewith may be withdrawn from the reactor and the composition of the gas passing through the reactor may be adjusted to maintain an essentially steady state gaseous composition within the reaction zone. The gas leaving the reaction zone may be passed to the velocity reduction zone where entrained particles are removed. Finer entrained particles and dust may be removed in a cyclone and / or fine filter. The gas may be passed through a heat exchanger where the heat of polymerization may be removed, compressed in a compressor, and then returned to the reaction zone. Additional reactor details and means for operating the reactor are described in, for example, U.S. Patent Nos. 3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400; 5,352,749; and 5,541,270; European Patent No. 0 802 202; and Belgian Patent No. 839,380.

[0136] In embodiments, the reactor temperature of the gas-phase polymerization reactor is less than or equal to 130 °C. For example, the reactor temperature of the gas-phase polymerization reactor may be from 30 °C to 120 °C, from 30 °C to 110 °C, from 30 °C to 100 °C, from 30 °C to 90 °C, from 30 °C to 80 °C, from 30 °C to 70 °C, from 30 °C to 60 °C, from 30 °C to 50 °C, from 30 °C to 40 °C, from 40 °C to 130 °C, from 40 °C to 120 °C, from 40 °C to 110 °C, from 40 °C to 100 °C, from 40 °C to 90 °C, from 40 °C to 80 °C, from 40 °C to 70 °C, from 40 °C to 60 °C, from 40 °C to 50 °C, from 50 °C to 130 °C, from 50 °C to 120 °C, from 50 °C to 110 °C, from 50 °C to 100 °C, from 50 °C to 90 °C, from 90 °C to 130 °C, from 90 °C to 120 °C, from 90 °C to 110 °C, from 90 °C to 100 °C, from 100 °C to85976-WO-PCT / DOW 85976 WO 130 °C, from 100 °C to 120 °C, from 100 °C to 110 °C, from 110 °C to 130 °C, from 110 °C to 120 °C, or from 120 °C to 130 °C. Generally, the gas-phase polymerization reactor may be operated at the highest temperature feasible, taking into account the sintering temperature of the polymer product within the reactor. Regardless of the process used for polymerization, the reactor temperature should be below the melting or “sintering” temperature of the polymer product. As a result, the upper temperature limit may be the melting temperature of the polymer product.

[0137] In embodiments, the reactor pressure of the gas-phase polymerization reactor is from 690 kPa (100 psig) to 3,448 kPa (500 psig). For example, the reactor pressure of the gas- phase polymerization reactor may be from 690 kPa (100 psig) to 2,759 kPa (400 psig), from 690 kPa (100 psig) to 2,414 kPa (350 psig), from 690 kPa (100 psig) to 1,724 kPa (250 psig), from 690 kPa (100 psig) to 1,379 kPa (200 psig), from 1,379 kPa (200 psig) to 3,448 kPa (500 psig), from 1,379 kPa (200 psig) to 2,759 kPa (400 psig), from 1,379 kPa (200 psig) to 2,414 kPa (350 psig), from 1,379 kPa (200 psig) to 1,724 kPa (250 psig), from 1,724 kPa (250 psig) to 3,448 kPa (500 psig), from 1,724 kPa (250 psig) to 2,759 kPa (400 psig), from 1,724 kPa (250 psig) to 2,414 kPa (350 psig), from 2,414 kPa (350 psig) to 3,448 kPa (500 psig), from 2,414 kPa (350 psig) to 2,759 kPa (400 psig), or from 2,759 kPa (400 psig) to 3,448 kPa (500 psig).

[0138] In embodiments, the ethylene partial pressure of the gas-phase polymerization reactor is from 207 kPa (30 psig) to 2,414 kPa (350 psig), though all individual values and subranges within the range of 207 kPa (30 psig) to 2,414 kPa (350 psig) are included. For example, in embodiments, the ethylene partial pressure of the gas-phase polymerization reactor may have a lower limit of 310 kPa (45 psig), 414 kPa (60 psig), 517 kPa (75 psig), 586 kPa (85 psig), 621 kPa (90 psig), or 655 kPa (95 psig). In embodiments, the ethylene partial pressure of the gas-phase polymerization reactor may have an upper limit of 2,068 kPa (300 psig), 1,655 kPa (240 psig), 1,517 kPa (220 psig), 1,379 kPa (200 psig), 1,034 kPa (150 psig), or 862 kPa (125 psig).

[0139] In embodiments, hydrogen gas may be used in during polymerization to control the final properties of the polyethylene. The amount of hydrogen used during polymerization may be expressed as a mole ratio relative to the total polymerizable monomer, such as, for example, ethylene or a blend of ethylene and 1-hexene. The amount of hydrogen used in the polymerization process may be an amount necessary to achieve the desired properties of the85976-WO-PCT / DOW 85976 WO polyethylene, such as, for example, melt flow rate. In embodiments, the mole ratio of hydrogen to total polymerizable monomer (H2:monomer) is greater than or equal to 0.0001. For example, the mole ratio of hydrogen to total polymerizable monomer (H2:monomer) may be from 0.0001 to 1.8, from 0.0001 to 1.0, from 0.0001 to 0.10, from 0.0001 to 0.001, from 0.0001 to 0.0005, from 0.0005 to 1.8, from 0.0005 to 1.0, from 0.0005 to 0.10, from 0.0005 to 0.001, from 0.001 to 1.8, from 0.001 to 1.0, from 0.001 to 0.10, from 0.001 to 0.05, or from 0.001 to 0.005.

[0140] The amount of hydrogen in the polymerization may also be expressed as a mole ratio relative to the molar amount of ethylene monomer. For example, the mole ratio of hydrogen to total ethylene monomer (H2:C2, or H2 / C2) may be from 0.0001 to 1.8, from 0.0001 to 1.0, from 0.0001 to 0.10, from 0.0001 to 0.001, from 0.0001 to 0.0005, from 0.0005 to 1.8, from 0.0005 to 1.0, from 0.0005 to 0.10, from 0.0005 to 0.001, from 0.001 to 1.8, from 0.001 to 1.0, from 0.001 to 0.10, from 0.001 to 0.05, or from 0.001 to 0.005.

[0141] In embodiments wherein at least one 1-alkene comonomer is used during polymerization, the ratio between the at least one 1-alkene comonomer to the ethylene monomer in the polymerization reactor may be from 0.0001 to 0.1, from 0.0001 to 0.05, from 0.0001 to 0.04, from 0.0001 to 0.03, from 0.0001 to 0.02, or from 0.0001 to 0.016. In embodiments, the ratio between the at least one 1-alkene comonomer to the ethylene monomer in the polymerization reactor may be from 0.0005 to 0.1, from 0.0005 to 0.05, from 0.001 to 0.05, from 0.001 to 0.04, from 0.001 to 0.03, from 0.001 to 0.02, from 0.001 to 0.016, or from 0.002 to 0.016.

[0142] In one or more embodiments, the polymerization process produces greater than or equal to 2,500 grams of the polyethylene per grams of the supported catalyst system per hour (gpoly / gcat·hour). In some embodiments, the process produces greater than or equal to 3,000 gpoly / gcat·hour, greater than or equal to 4,000 gpoly / gcat·hour, greater than or equal to 5,000 gpoly / gcat·hour, greater than or equal to 6,000 gpoly / gcat·hour, greater than or equal to 7,000 gpoly / gcat·hour, greater than or equal to 8,000 gpoly / gcat·hour, greater than or equal to 9,000 gpoly / gcat·hour, greater than or equal to 10,000 gpoly / gcat·hour, greater than or equal to 11,000 gpoly / gcat·hour, greater than or equal to 12,000 gpoly / gcat·hour, greater than or equal to 13,000 gpoly / gcat·hour, greater than or equal to 14,000 gpoly / gcat·hour, greater than or equal to 15,000 gpoly / gcat·hour, greater than or equal to 20,000 gpoly / gcat·hour, greater than or equal to 25,000 gpoly / gcat·hour, greater than or equal to 30,000 gpoly / gcat·hour, greater than or equal to 35,00085976-WO-PCT / DOW 85976 WO gpoly / gcat·hour, greater than or equal to 40,000 gpoly / gcat·hour, or greater than or equal to 45,000 gpoly / gcat·hour.

[0143] Polyolefins

[0144] In embodiments, the supported catalyst systems of the present disclosure may be utilized to polymerize a single type of olefin, producing a homopolymer. However, additional 1-alkenes (also called alpha-olefins) may be incorporated into the polymerization scheme in other embodiments. The additional 1-alkene comonomers typically have no more than 20 carbon atoms. For example, the supported catalyst systems of the present disclosure may be utilized to polymerize ethylene monomer and at least one 1-alkene comonomer. Exemplary 1-alkene comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1- hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-l-pentene. For example, the at least one 1-alkene comonomer may be selected from the group consisting of propylene, 1- butene, 1-hexene, and 1-octene; or, in the alternative, from the group consisting of 1-hexene and 1-octene. In embodiments, the at least one 1-alkene comonomer comprises 1-butene or 1-hexene.

[0145] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a weight average molecular weight of greater than or equal to 30,000 g / mol and less than or equal to 400,000 g / mol, greater than or equal to 50,000 g / mol and less than or equal to 400,000 g / mol, greater than or equal to 70,000 g / mol and less than or equal to 400,000 g / mol, greater than or equal to 90,000 g / mol and less than or equal to 400,000 g / mol, greater than or equal to 110,000 g / mol and less than or equal to 400,000 g / mol, greater than or equal to 130,000 g / mol and less than or equal to 400,000 g / mol, or greater than or equal to 150,000 g / mol and less than or equal to 400,000 g / mol.

[0146] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a comonomer incorporation as determined by Rapid FT-IR (Fourier Transformer Infrared) spectroscopy of the dissolved polymer as part of the GPC measurement of greater than or equal to 1 wt%, greater than or equal to 2 wt%, greater than or equal to 3 wt%, greater than or equal to 5 wt%, greater than or equal to 7 wt%, greater than or equal to 8 wt%, greater than or equal to 9 wt%, greater than or equal to 10 wt%, greater than or equal to 11 wt%, greater than or equal to 12 wt%,85976-WO-PCT / DOW 85976 WO greater than or equal to 13 wt%, greater than or equal to 14 wt%, greater than or equal to 15 wt%, greater than or equal to 16 wt%, greater than or equal to 20 wt%, or greater than or equal to 21 wt%.

[0147] Most ethylene-based copolymers have comonomer contents (i.e., weight fraction amounts of constituent units derived from the 1-alkene that are in the copolymer) that vary with molecular weight of the constituent macromolecules thereof. Basically, if a higher molecular weight fraction of macromolecules has lower wt% comonomer content, this is a normal comonomer distribution versus molecular weight. The normal comonomer distribution may also be referred to as a normal short-chain branching distribution (normal SCBD) or normal molecular weight comonomer distribution index (normal MWCDI). If MWCDI is less than 0, there is a normal MWCDI or normal SCBD. If MWCDI = 0, there is a flat MWCDI or flat SCBD. The MWCDI value is determined from a plot of SCB per 1000 carbon atoms versus Log(GPC Flory distribution of molecular weight) (Log(MW)). See U.S. Patent Application Publication No. 2024 / 0081444 A1.

[0148] When a higher molecular weight fraction has higher wt% comonomer content than the lower molecular weight fraction, then it would be said to have a reverse comonomer distribution versus molecular weight. This phenomenon is also referred to as a reverse short- chain branching distribution (reverse SCBD), reverse molecular weight comonomer distribution index (reverse MWCDI), or broad-orthogonal composition distribution (BOCD). If MWCDI is greater than 0, there is a reverse comonomer distribution or reverse SCBD. In embodiments, the poly(ethylene-co-1-alkene) copolymer produced from the methods described herein comprises a reverse comonomer distribution. In embodiments, the poly(ethylene-co-1-alkene) copolymer produced from the methods described herein comprises broad orthogonal comonomer or composition distribution as defined by a molecular weight comonomer distribution index greater than zero.

[0149] These comonomer content distributions across molecular weights are shown by plotting a linear regression of the comonomer content in weight percent (wt%) on a y-axis versus Log(MW) on an x-axis. The wt% comonomer content is determined by rapid Fourier Transform-Infrared (FT-IR) spectroscopy on dissolved copolymer in a gel permeation chromatography (GPC) measurement using an infrared detector. MW is the specific x-axis molecular weight point (10 ^ [Log(MW)]) of a Flory distribution of molecular weight, as measured by GPC. In such a plot, the normal comonomer distribution has a negative slope85976-WO-PCT / DOW 85976 WO (i.e., a line fitted to data points going from lower Log(MW) values to higher Log(MW) values (from left to right on the x-axis) slopes downward).

[0150] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein comprises units derived from the ethylene monomer making up at least 50 wt% of the poly(ethylene-co-1-alkene) copolymer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer. For example, the poly(ethylene-co-1-alkene) copolymer may comprise units derived from the ethylene monomer making up at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt% at least 90 wt%, at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt% of the poly(ethylene-co-1-alkene) copolymer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer. In embodiments, the poly(ethylene-co-1-alkene) copolymer comprises units derived from the ethylene monomer making up from 50 to 99.9 wt%, from 60 to 99.9 wt%, from 70 to 99.9 wt%, from 80 to 99.9 wt%, from 90 to 99.9 wt%, from 95 to 99.9 wt%, from 96 to 99.9 wt%, from 97 to 99.9 wt%, from 98 to 99.9 wt%, or from 99 to 99.9 wt%, of the poly(ethylene-co-1-alkene) copolymer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer.

[0151] In embodiments, the poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein comprises units derived from the at least one 1-alkene comonomer making up at least 50 wt% of the poly(ethylene-co-1-alkene) copolymer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer. For example, the poly(ethylene-co-1-alkene) copolymer may comprise units derived from the at least one 1-alkene comonomer making up at least 0.1 wt%, at least 0.5 wt%, at least 1.0 wt%, at least 1.5 wt%, at least 2.0 wt%, at least 3.0 wt%, at least 4.0 wt%, at least 5.0 wt%, at least 6.0 wt%, at least 7.0 wt%, at least 9.0 wt%, at least 9.0 wt%, at least 10 wt%, at least 11 wt%, at least 12 wt%, at least 13 wt%,at least 15 wt%, or at least 21 wt% of the poly(ethylene-co- 1-alkene) copolymer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer. the poly(ethylene-co-1-alkene) copolymer may comprise units derived from the at least one 1-alkene comonomer making up at most 50 wt%, at most 40 wt%, at most 30 wt%, at most 20 wt% or at most 10 wt% of the poly(ethylene-co-1-alkene) copolymer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer. In embodiments, the poly(ethylene-co- 1-alkene) copolymer comprises units derived from the at least one 1-alkene comonomer making up from 0.1 to 50 wt%, from 0.5 to 50 wt%, from 1.0 to 50 wt%, from 1.0 to 40 wt%,85976-WO-PCT / DOW 85976 WO from 1.0 to 30 wt%, from 1.0 to 25 wt%, from 1.0 to 20 wt%, or from 1.0 to 15% of the poly(ethylene-co-1-alkene) copolymer, based on a total weight of the poly(ethylene-co-1- alkene) copolymer.

[0152] In embodiments, the poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein comprises deactivated derivative of the phosphinimine procatalyst making up from 0.0001 ppm to 10,000 ppm, based on a total weight of the poly(ethylene-co-1-alkene) copolymer, though all individual values and subranges within the range of 0.0001 ppm to 10,000 ppm are included. For example, in embodiments, the poly(ethylene-co-1-alkene) copolymer can include from a lower limit of the deactivated derivative of the phosphinimine procatalyst of 0.0001, 0.001, or 0.01 ppm, and an an upper limit of 10,000 ppm, 5,000 ppm, 1,000 ppm, or 500 ppm. The amount, e.g., ppm, of the deactivated derivative of the phosphinimine procatalyst can be determined by calculating the amount (mass) of polymer produced or calculated to be produced using ethylene and comonomer uptake, or consumption, divided by the amount (mass) of active Group IV catalyst used represented by formula (I), and then multiplied by 1,000,000.

[0153] The deactivated derivative of the phosphinimine procatalyst, as discussed herein, is made from a polymerization process, as discussed herein, which utilizes the supported catalyst system containining the activated phosphinimine Group IV catalyst of structure (I). In other words, when making the poly(ethylene-co-1-alkene) copolymers disclosed herein, the activated supported catalyst systems containing the phosphinimine Group IV catalyst can be subjected to polymerization conditions, including conditions during or after the polymerization process, to make the deactivated form of or a deactivated derivative of the phosphinimine procatalyst from the activated supported catalyst system.

[0154] In embodiments, the poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein comprises deactivated derivative of the phosphinimine catalyst making up from 0.0001 ppm to 5,000 ppm, from 0.0001 ppm to 1,000 ppm, from 0.0001 ppm to 500 ppm, from 0.0001 ppm to 100 ppm, from 0.0001 ppm to 50 ppm, from 0.0001 ppm to 10 ppm, from 0.0001 ppm to 5 ppm, from 0.001 ppm to 5 ppm, from 0.01 ppm to 5 ppm, from 0.05 ppm to 5 ppm, from 0.1 ppm to 5 ppm, or from 0.1 ppm to 5 ppm of the poly(ethylene-co-1-alkene) copolymer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer. The deactivated derivative of the phosphinimine85976-WO-PCT / DOW 85976 WO procatalyst is produced, in part, by subjecting the supported catalyst system to the polymerization conditions.

[0155] As described above, in embodiments, a method of making a poly(ethylene-co-1- alkene) copolymer comprises polymerizing, via gas-phase polymerization, ethylene monomer and at least one 1-alkene comonomer in the presence of the supported catalyst system including a support material, an activator, a phosphinimine of formula (I), and a metallocene of one of formulas (IIa)–(IIc). In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a density according to ASTM D792 (incorporated herein by reference in its entirety) from 0.850 g / cm3to 0.960 g / cm3, from 0.880 g / cm3to 0.920 g / cm3, from 0.880 g / cm3to 0.910 g / cm3, or from 0.880 g / cm3to 0.900 g / cm3, for example.

[0156] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a melt index (I2) according to ASTM 1238, Condition B (190 °C, 2.16 kg) (incorporated herein by reference in its entirety) of less than or equal to 0.5 dg / min, less than 0.4 dg / min, less than 0.3 dg / min, less than 0.25 dg / min, less than 0.2 dg / min, or less than 0.1 dg / min, with an MWCDI > 0.0.

[0157] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a melt flow ratio (I21 / I2) of greater than or equal to 20, greater than or equal to 25, greater than or equal to 30, greater than or equal to 35, greater than or equal to 40, greater than or equal to 45, greater than or equal to 50, greater than or equal to 55, greater than or equal to 60, greater than or equal to 65, greater than or equal to 70, greater than or equal to 75, or greater than or equal to 80, wherein the melt index (I2) and high load melt flow index (I21) are measured according to ASTM 1238, condition B (190 °C, 2.16 kg for I2and 21.6 kg for I21), with an MWCDI > 0.0.

[0158] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a melt index (I2) of less than 0.5 dg / min and a melt flow ratio (I21 / I2) of greater than or equal to 25, wherein the melt index (I2) and high load flow melt index (I21) are measured according to ASTM 1238, condition B (190 °C, 2.16 kg for I2 and 21.6 kg for I21), with an MWCDI > 0.0.

[0159] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a melt index (I2) of less than85976-WO-PCT / DOW 85976 WO 0.5 dg / min and a melt flow ratio (I21 / I2) of greater than or equal to 25, wherein the melt index (I2) and high load flow melt index (I21) are measured according to ASTM 1238, condition B (190 °C, 2.16 kg for I2 and 21.6 kg for I21), with an MWCDI > 0.0, wherein the supported catalyst system acheives a productivity greater than or equal to 10,000 gpoly / gcat·hour.

[0160] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a melt index (I2) according of greater than 40 dg / min wherein the melt index (I2) is measured according to ASTM 1238, condition B (190 °C, 2.16 kg), with an MWCDI > 0.0, wherein the supported catalyst system acheives a productivity greater than or equal to 10,000 gpoly / gcat·hour.

[0161] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a polydispersity index (PDI, Mw / Mn) greater than or equal to 3.0 and an MWCDI > 0.0, wherein the supported catalyst system acheives a productivity greater than or equal to 10,000 gpoly / gcat·hour, where Mw is the weight average molecular weight and Mn is the number average molecular weight.

[0162] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a Mz / Mw greater than or equal to 3.0, greater than or equal to 3.5, greater than or equal to 4.0, greater than or equal to 4.5, greater than or equal to 5.0, greater than or equal to 5.5, or greater than or equal to 6.0. In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a Mz / Mw greater than or equal to 3.0 and a MWCDI > 0.0, wherein the supported catalyst system acheives a productivity greater than or equal to 10,000 gpoly / gcat·hour, where Mz is the z-average molecular weight. Without wishing to be bound by theory, it is believed that the combination of Mz / Mw ≥ 3.0 and MWCDI > 0.0 provides improved mechanical, toughness, and abuse properties as well as higher melt strength for the final resin.

[0163] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a Mz / Mw greater than or equal to 3.5 and an MWCDI > 0.0, wherein the supported catalyst system acheives a productivity greater than or equal to 10,000 gpoly / gcat·hour. The combination of Mz / Mw ≥ 3.5 and MWCDI > 0.0 may further improve mechanical, toughness, and abuse properties as well as achieve higher melt strength for the final resin. In embodiments, a poly(ethylene-co-1-alkene)85976-WO-PCT / DOW 85976 WO copolymer polymerized in the presence of a supported catalyst system described herein has a Mz / Mw greater than or equal to 4.0 and an MWCDI > 0.0, wherein the supported catalyst system acheives a productivity greater than or equal to 10,000 gpoly / gcat·hour. The combination of Mz / Mw ≥ 4.0 and MWCDI > 0.0 may further improve mechanical, toughness, and abuse properties as well as achieve higher melt strength for the final resin. In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a Mz / Mw greater than or equal to 4.5 and an MWCDI > 0.0, wherein the supported catalyst system acheives a productivity greater than or equal to 10,000 gpoly / gcat·hour. The combination of Mz / Mw ≥ 4.5 and MWCDI > 0.0 may further improve mechanical, toughness, and abuse properties as well as achieve higher melt strength for the final resin. In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a Mz / Mw greater than or equal to 5.0 and an MWCDI > 0.0, wherein the supported catalyst system acheives a productivity greater than or equal to 10,000 gpoly / gcat·hour. The combination of Mz / Mw ≥ 5.0 and MWCDI > 0.0 may further improve mechanical, toughness, and abuse properties as well as achieve higher melt strength for the final resin. In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a Mz / Mw greater than or equal to 5.5 and an MWCDI > 0.0, wherein the supported catalyst system acheives a productivity greater than or equal to 10,000 gpoly / gcat·hour. The combination of Mz / Mw ≥ 5.5 and MWCDI > 0.0 may further improve mechanical, toughness, and abuse properties as well as achieve higher melt strength for the final resin. In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a supported catalyst system described herein has a Mz / Mw greater than or equal to 6.0 and an MWCDI > 0.0, wherein the supported catalyst system acheives a productivity greater than or equal to 10,000 gpoly / gcat·hour. The combination of Mz / Mw ≥ 6.0 and MWCDI > 0.0 may further improve mechanical, toughness, and abuse properties as well as achieve higher melt strength for the final resin.

[0164] The ethylene-based polymers, e.g., homopolymers and / or poly(ethylene-co-1- alkene) copolymers, may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymers may contain any amounts of additives. The ethylene-85976-WO-PCT / DOW 85976 WO based polymers may compromise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the ethylene-based polymers and the one or more additives. The ethylene-based polymers may further comprise fillers, which may include, but are not limited to, organic or inorganic fillers. The ethylene-based polymers may contain from about 0 to about 20 weight percent fillers such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the combined weight of the ethylene-based polymers and all additives or fillers. The ethylene-based polymers may further be blended with one or more polymers to form a blend.

[0165] The produced polyethylene may be used in a wide variety of products and end-use applications. The produced polyethylene may also be blended and / or co-extruded with any other polymer. Non-limiting examples of other polymers include linear low density polyethylene, elastomers, plastomers, high pressure low density polyethylene, high density polyethylene, polypropylenes, and the like. The produced polyethylene and blends including the produced polyethylene may be used to produce blow-molded components or products, pipes, films, injection molded or rotomolded products, among various other end uses. The produced polyethylene and blends including the produced polyethylene may be useful in forming operations such as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding. Films may include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, and membranes in food-contact and non-food contact applications. Fibers may include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, and geotextiles. Extruded articles may include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners. Molded articles may include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys.

[0166] Embodiments of the catalyst systems described in this disclosure yield unique polymer properties as a result of the range of weight average molecular weights, including high molecular weights of the polymers formed combined with the broad melt flow ratios (I21 / I2) and molecular weight distributions (PDI), the amount of the comonomers incorporated85976-WO-PCT / DOW 85976 WO into the polymers, the reverse short chain branching distribution (MWCDI > 0.0), and broad Mz / Mw (≥ 3.0).

[0167] One or more features of the present disclosure are illustrated in view of the examples as follows: EXAMPLES Example 1: Synthesis of MLC-1MLC-1

[0168] In a N2-filled glovebox, the chloro complex (262 mg, 0.61 mmol, 1 equivalents) was dissolved in 5 mL of toluene. To this yellow-colored solution was added MeMgBr (0.471 mL of 3 (M)in hexanes, 1.4 mmol, 2.3 equivalents) causing the solution color to change to a dark yellow color and also causing precipitation. After 0.5 h of stirring at ambient temperature, the reaction mixture was filtered through Whatman syringe filter. The filtrate was evaporated to afford yellow solid. The yellow solid was dissolved in minimum amount of toluene (0.5 mL) and 2 mL of hexane was added followed by filtration to get rid of the Mg-salts. The filtrate was removed under vacuum to yield crystalline yellow solid (170 mg, 72%).

[0169] 1H NMR (500 MHz, C6D6) δ 6.22 (s, 4H), 2.34 – 2.23 (m, 2H), 2.01 – 1.88 (m, 1H), 1.70 – 1.58 (m, 2H), 1.53 (d, J = 7.1 Hz, 1H), 1.34 – 1.20 (m, 2H), 1.17 (d, J = 13.2 Hz, 18H), 1.10 – 0.93 (m, 3H), 0.67 (s, 6H).31P NMR (202 MHz, C6D6) δ 25.05.13C NMR (126 MHz, C6D6) δ 110.76, 41.27, 40.88, 39.93, 39.40, 38.99, 29.80, 28.10, 26.68. Example 2: Synthesis of the dichloride complex intermediate to MLC-185976-WO-PCT / DOW 85976 WO

[0170] In a continuous purge N2-filled glovebox, 1,1-di-tert-butyl-1-cyclohexyl-N- (trimethylsilyl)-λ5-phosphanimine (111 mg, 0.51 mmol, 1 equivalents) and cyclopentadienyltitanium trichloride (160 mg, 0.51mmol, 1 equivalents) were dissolved in 5 mL of toluene to give a cloudy yellow mixture which was heated at 80 °C for 2 h. Toluene was removed under reduced pressure to afford yellow solid. Hexane (5 mL) was added to the yellow solid and the solid was stirred for 10 mins followed by filtration through a frit funnel yielded yellow powder. The yellow powder was washed with hexanes (2 mL x 2) to yield the desired product (262 mg, quantitative yield). The material was used in the subsequent reaction without further purification.

[0171] 1H NMR (500 MHz, C6D6) δ 6.45 (s, 4H), 2.16 (dd, J = 13.0, 5.7 Hz, 2H), 2.01 (dtt, J = 15.1, 12.4, 2.6 Hz, 1H), 1.64 – 1.38 (m, 3H), 1.10 (d, J = 14.1 Hz, 21H), 1.06 – 0.84 (m, 2H).31P NMR (202 MHz, C6D6) δ 39.00. Example 3: Synthesis of the intermediate to MLC-1

[0172] In a continuous purge N2-filled glovebox, a 50 mL vial was charged with di-tert- butylcyclohexylphosphine (1.0 g, 4.4 mmol, 1 equivalents), trimethylsilyl azide (0.61 g, 5.3 mmol, 1.2 equiv), and the reaction mixture was heated at 80 °C for 4 hr.31PNMR revealed clean formation of the desired product. Trimethylsilyl azide was removed under reduced pressure at ambient temperature for 1 h to afford colorless product as an oil (178 mg, 13% yield).

[0173] 1H NMR (500 MHz, C6D6) δ 2.25 – 2.15 (m, 2H), 1.78 – 1.63 (m, 2H), 1.60 – 1.55 (m, 1H), 1.32 – 1.21 (m, 2H), 1.20 – 1.01 (m, 22H), 0.41 (s, 9H).31P NMR (202 MHz, C6D6) δ 27.09.13C NMR (126 MHz, C6D6) δ 41.61, 41.18, 38.11, 37.64, 30.04, 30.02, 28.51, 28.42, 28.17, 26.92, 4.95.85976-WO-PCT / DOW 85976 WO

[0174] In a continuous purge N2-filled glovebox, the dichloride complex (200 mg, 0.35 mmol, 1 equivalents) was dissolved in 5 mL of toluene. To this yellow-colored solution was added MeMgBr (0.270 mL of 3 (M) in Et2O, 0.81 mmol, 2.3 equivalents) changing the solution color to dark yellow and causing precipitation. After 20 min of stirring at ambient temperature, the reaction mixture was filtered. The filtrate was evaporated to afford dark yellow solid. The dark yellow solid was dissolved in minimum amount of toluene (0.5 mL) and 2 mL of hexane was added followed by filtration. The filtrate was removed under vacuum to yield a dark yellow solid (110 mg, 60%).

[0175] 1H NMR (400 MHz, C6D6) δ 6.95 – 6.91 (m, 2H), 6.00 (t, J = 2.8 Hz, 2H), 1.17 (d, J = 13.0 Hz, 27H), 0.57 (s, 6H).19F NMR (376 MHz, C6D6) δ -140.28 – -140.75 (m), -159.61, -163.95.31P NMR (162 MHz, C6D6) δ 33.50.13C NMR (101 MHz, C6D6) δ 146.61 – 143.34 (m), 140.25 – 136.76 (m), 112.95 (s), 112.48 (t, J = 7.7 Hz), 110.42 (s), 42.64 (s), 41.56 (s), 41.10 (s), 29.54 (s). Example 5: Synthesis of MLC-385976-WO-PCT / DOW 85976 WO

[0176] In a continuous purge N2-filled glovebox, 1,1,1-tri-tert-butyl-N-(trimethylsilyl)- λ5- phosphanimine (195 mg, 0.67 mmol, 1 equivalents) was dissolved in 2 mL of toluene to give a clear colorless solution. The trichloride complex (260 mg, 0.67 mmol, 1 equivalents) was dissolved in 2 mL Toluene. The phosphanimine solution was added to the titanium precursor dropwise, and then heated for 16 hr at 60 °C to afford a homogeneous orange solution. After stirring at 60 °C for 16 hr, the reaction mixture was cooled down to ambient temperature. Toluene was removed under vacuum to afford a yellow solid. The yellow solid was filtered and washed with hexanes (2 x 5mL), and dried under vacuum to yield yellow powder (330 mg, 87 %).

[0177] 1H NMR (500 MHz, C6D6) δ 7.01 (tt, J = 3.1, 1.6 Hz, 2H), 6.51 (t, J = 2.8 Hz, 2H), 1.12 (d, J = 13.8 Hz, 27H).19F NMR (471 MHz, C6D6) δ -139.27, -157.06, -163.66.31P NMR (202 MHz, C6D6) δ 47.68.13C NMR (126 MHz, C6D6) δ 146.55 – 144.15 (m), 141.04 – 138.55 (m), 139.50 – 137.12 (m), 118.76 (s), 115.81 (t, J = 7.3 Hz), 113.34 (s), 111.28 (td, J = 13.5, 4.1 Hz), 42.07 (d, J = 42.9 Hz), 29.42 (s), 29.11 (s). Example 6: Synthesis of the trichloride intermediate to MLC-2 and -3

[0178] In a continuous purge N2-filled glove box, (TMS)(C6F5)C5H3 (800 mg, 2.6 mmol, 0.83 equivalents) was added to titanium tetrachloride (600 mg, 3.16 mmol, 1 equivalents) dropwise, the color changed to a dark orange color, and the solution was heated to 60°C for 3 h. The reaction mixture was cooled down to room temperature. Hexanes (3 mL) was added to the reaction mixture. A bright orange precipitate formation was observed. The precipitate was filtered through a fritted funnel and the residue was washed with 10 mL hexanes twice. The residue was dried under vacuum to afford orange solid (530 mg, 52%).

[0179] 1H NMR (500 MHz, C6D6) δ 6.66 (tt, J = 2.8, 1.3 Hz, 2H), 6.07 (t, J = 2.9 Hz, 2H).19F NMR (471 MHz, C6D6) δ -138.04 (dt, J = 20.6, 5.6 Hz), -150.71 – -151.20 (m), -160.89 – -161.35 (m).13C NMR (126 MHz, C6D6) δ 145.96 – 143.95 (m), 142.99 – 140.41 (m),85976-WO-PCT / DOW 85976 WO 139.33 – 136.89 (m), 125.12 (q, J = 2.6 Hz), 122.98 (s), 122.20 (t, J = 7.2 Hz), 108.56 (td, J = 13.2, 4.3 Hz). Example 7: Synthesis of the intermediate to MLC-2 and -3

[0180] In a continuous purge N2-filled glovebox, a 100 mL Round Bottom flask was containing sodium cyclopentadiene (2(M) THF solution (25 mL, 50 mmol, 1 equivalents) was added a solution of hexafluorobenzene (2.9 mL, 25 mmol, 0.5 equivalents) in 3 mL of THF dropwise over 5 mins. The dark green colored solution was heated to 60 °C for 3 hrs. Chlorotrimethylsilane (4.4 mL, 0.035 mmol, 0.7 equiv) was added slowly over 5 mins, then stirred under N2overnight. The volatiles were removed under vacuum, the solid was triturated twice with 10 mL of hexane, filtered, and then washed with hexane (5x3 mL). Hexane was removed under vacuum yielding brown liquid which was distilled under full vacuum at 115 °C. A clear colorless liquid was obtained (3.2 g, 42%).

[0181] 1H NMR (500 MHz, C6D6) δ 6.94 – 6.34 (m, 3H), 3.55 – 2.82 (m, 1H), 0.21 – 0.12 (m, 1H), -0.13 (s, 9H). Example 8: Synthesis of the tri-tert-butylphosphinimine intermediate for MLC-2 and -3

[0182] In a continuous purge N2-filled glovebox, a 50 mL vial was charged with tri-tert- butylphosphine (1.8 g, 8.9 mmol, 1 equivalents) followed by the addition of TMS-azide (1.23 g, 10.7 mmol, 1.2 equiv), and the reaction mixture was heated at 90°C for 8 h. Excess TMS- azide was removed under reduced pressure and the desired product was obtained as a white solid (2 g, 78%).

[0183] 1H NMR (500 MHz, C6D6) δ 1.15 (d, J = 12.6 Hz, 27H), 0.41 (s, 9H).31P NMR (202 MHz, C6D6) δ 32.26 (ttq, J = 37.9, 25.3, 12.9 Hz).85976-WO-PCT / DOW 85976 WO Example 9: Synthesis of MLC-4

[0184] In a continuous purge N2-filled glovebox, a 20 mL vial was charged with the dichloride complex (244 mg, 0.53 mmol, 1 equivalents), 5 mL of toluene, and a stir bar. MeMgBr (0.407 mL of 3 (M) MeMgBr in Et2O, 1.2 mmol, 2.3 equivalents) was added to the solution, and the reaction mixture was stirred for 30 min at ambient temperature. The color of the solution changed from yellow to dark yellow upon addition of MeMgBr. The reaction mixture was filtered through a frit funnel after 30 min. Toluene was removed under reduced pressure. To the yellow-colored solid residue was added a 1:2 mixture toluene:hexanes (10 mL). The slurry was filtered through a frit funnel, followed by hexanes wash (2 x 5 ml). Solvent was removed from the filtrate to afford yellow powder (173 mg, 78%).

[0185] 1H NMR (500 MHz, C6D6) δ 7.87 – 7.70 (m, 6H), 7.04 (d, J = 7.3 Hz, 9H), 6.04 (d, J = 2.3 Hz, 5H), 0.94 (d, J = 2.4 Hz, 6H).31P NMR (202 MHz, C6D6) δ -7.90.13C NMR (126 MHz, C6D6) δ 134.36, 133.57, 132.51, 132.43, 131.57, 131.54, 128.68, 128.58, 111.17, 43.29. Example 10: Synthesis of the intermediate to MLC-4

[0186] In a continuous purge N2-filled glovebox, a 50 mL vial was charged with cylopentadienyltitanium(IV) trichloride (200 mg, 0.91 mmol, 1 equivalents), 1,1,1-triphenyl- N-(trimethylsilyl)-λ5-phosphanimine (318 mg, 0.91 mmol, 1 equivalents) and 5 mL of toluene to give a cloudy yellow mixture. Heating for 2 h at 80 °C afforded a heterogeneous yellow solution. The reaction mixture was cooled down to ambient temperature after 2 h. Toluene was removed under vacuum. To the yellow solid residue, 7 mL of hexanes was added. The residue was filtered through a frit funnel, followed by washing with hexanes (2 x 5 mL). The residue was dried under reduced pressure to yield yellow powder (335 mg, 80%).85976-WO-PCT / DOW 85976 WO

[0188] In a continuous purge nitrogen filled glovebox, to a stirring (500 rpm) slurry of HfCl4 (92.8 mg, 0.2896 mmol, 1.00 eq) in anhydrous deoxygenated THF (10 mL) was added a solution of the dilithio salt (100.0 mg, 0.3040 mmol, 1.05 eq) in THF (4 mL, rinse 3 x 2 mL). The resultant golden yellow solution was stirred (500 rpm) for 18 hrs. The resultant pale- yellow solution was concentrated, suspended in hexanes (10 mL), stirred (500 rpm) for 5 mins, suction filtered through a fritted filter, rinsed with hexanes (4 x 10 mL), concentrated, the resultant golden yellow amorphous foam was suspended in hexanes (10 mL), suction filtered through a fritted filter, rinsed with hexanes (4 x 10 mL), and concentrated. The resultant pale-golden yellow oil was suspended in pentane (10 mL), placed in the freezer (- 35 °C) for 4 hrs, filtered cold using a double 0.45 µm PTFE filter, rinsed with cold pentane (3 x 5 mL), and concentrated. The resultant golden yellow oil was suspended in pentane (10 mL), placed in the freezer for 18 hrs, filtered cold using a double 0.45 µm PTFE filter, rinsed with cold pentane (4 x 5 mL), and concentrated to provide Example 2, observed to be a pale- yellow oil (95.4 mg, 0.1686 mmol, 58%). NMR indicated product exists as a mixture of rac- and meso isomers. *Denotes chemical shifts of the meso isomer.1H NMR (500 MHz, C6D6) δ 6.59 – 6.56 (m, 2H), *6.53 – 6.49 (m, 2H), *5.57 (t, J = 2.7 Hz, 2H), 5.43 (t, J = 2.7 Hz, 2H), 5.25 (t, J = 2.4 Hz, 2H), *5.16 (t, J = 2.3 Hz, 2H), 2.88 – 2.70 (m, 4H), 1.61 – 1.47 (m, 4H), 0.87 (td, J = 7.4, 5.5 Hz, 6H), *0.33 (s, 3H), 0.29 (s, 6H), 0.26 (s, 3H).13C NMR (126 MHz, C6D6) δ *140.01, 139.99, *125.30, 124.83, *111.29, 111.22, *110.74, 110.43, *107.83, 107.70, 32.25, *23.67, 23.62, 13.85, *13.83, *-6.18, -6.22, *-6.24.85976-WO-PCT / DOW 85976 WO Example 12: Synthesis of the intermediate to MLC-7:

[0189] In a continuous purge nitrogen filled glovebox, a pale golden yellow solution of the starting bis-cyclopentadiene (0.303 g, 0.9524 mmol, 1.00 eq) in anhydrous deoxygenated Et2O (10 mL) was placed in a freezer (-35 °C) for 16 hrs, and then n-BuLi (0.86 mL, 2.143 mmol, 2.25 eq, 2.5 M in hexanes) was added. The resultant white heterogeneous mixture was maintained in the freezer for 30 mins, removed from the freezer, and stirred (500 rpm) at 23 °C for 2 hrs. The white mixture was suction filtered, the white solid was rinsed with Et2O (4 x 10 mL), and dried in vacuo to provide the dilithio salt, which was observed to be a white solid (0.273 g, 0.8269 mmol, 87%). NMR (in THF & C6D6) indicated product.1H NMR (400 MHz, C6D6 with THF) δ 6.05 – 6.02 (m, 2H), 5.94 (t, J = 2.1 Hz, 2H), 5.91 (t, J = 2.6 Hz, 2H), 2.69 – 2.60 (m, 4H), 1.75 – 1.66 (m, 4H), 1.05 – 0.99 (m, 6H), 0.63 (s, 6H). Example 13: Synthesis of an intermediate to MLC-7:

[0190] In a continuous purge nitrogen filled glovebox, a red-orange mixture of PrCpLi (0.250 g, 2.191 mmol, 2.25 eq) in anhydrous deoxygenated THF (15 mL) was placed in a freezer (-35 °C) for 12 hrs, and then neat Me2GeCl2(0.11 mL, 0.9738 mmol, 1.00 eq) was added. The red-orange mixture was allowed to sit in the freezer for 30 mins, removed, and the red-orange solution was stirred (500 rpm) at 23 °C for 4 hrs. The solution was concentrated, suspended in hexanes (5 mL), and concentrated. The mixture was suspended in hexanes (10 mL), stirred (500 rpm) for 2 mins, suction filtered through Celite, rinsed with hexanes (4 x 10 mL), concentrated, the filtrate was suspended in hexanes (10 mL), filtered through a double 0.45 µm PTFE filter, rinsed with hexanes (3 x 3 mL), and concentrated to provide the bridged bis-cyclopentadiene, which was observed to be a clear golden yellow oil85976-WO-PCT / DOW 85976 WO (0.303 g, 0.9524 mmol, 98%). NMR indicated product exists as a mixture of isomers.1H NMR (400 MHz, C6D6) δ 6.82 – 5.91 (m, 6H), 4.31 – 2.83 (m, 2H), 2.39 (t, J = 7.6 Hz, 4H), 1.57 (h, J = 7.4 Hz, 4H), 0.92 (t, J = 7.4 Hz, 6H), -0.08 (s, 6H).

[0191] Synthesis procedures for MLC-5 are known by those skilled in the art, e.g., as described in International Publication No. WO2020 / 223144 A1. Further, metallocene catalyst MLC-6 is commercially available from several commercial suppliers and synthesized by those skilled in the art as described in International Publication No. WO2008002524 A2.

[0192] 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 3Å molecular sieves. Glassware for moisture-sensitive reactions was dried in an oven overnight prior to use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analyses were performed using a Waters e2695 Separations Module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separations were performed on an XBridge C183.5 μm 2.1x50 mm column using a 5:95 to 100:0 acetonitrile to water gradient with 0.1% formic acid as the ionizing agent. HRMS analyses were performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8μm 2.1x50 mm column coupled with an Agilent 6230 TOF Mass Spectrometer with electrospray ionization.1H NMR data are reported as follows: chemical shift (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sex = sextet, sept = septet and m = multiplet), integration, and assignment). Chemical shifts for1H NMR data are reported in ppm downfield from internal tetramethylsilane (TMS, δ scale) using residual protons in the deuterated solvent as references.13C NMR data were determined with1H decoupling, and the chemical shifts are reported downfield from tetramethylsilane (TMS, δ scale) in ppm versus the using residual carbons in the deuterated solvent as references.

[0193] Procedure for Preparing Spray-Dried Catalyst Systems

[0194] Spray-dried catalyst samples SD-SCS-1 through -4 were prepared and sprayed in a nitrogen-purged glove box. In an oven-dried jar, Cabosil™ TS-610 fumed silica was slurried in toluene until well dispersed, then a 10 % solution by weight of MAO in toluene was added.85976-WO-PCT / DOW 85976 WO The mixture was stirred magnetically for 15 minutes, then the metal-ligand complex was added to the resulting slurry, and the mixture was stirred for 30-60 minutes. The mixture was spray-dried using a Buchi Mini Spray Dryer B-290 with the following parameters to yield the dried sample: Set Temperature: 140 °C, Outlet Temperature: 75 °C (min.), aspirator setting of 60 rotations per minute (rpm), and pump speed of 130 rpm. Table 1 contains the amounts of the metal-ligand complex (MLC), fumed silica, 10% MAO solution, and toluene used to make each of the spray-dried catalysts systems.

[0195] Spray-dried catalyst samples SD-SCS-5 through -8 were prepared and sprayed in a nitrogen-purged glove box. In an oven-dried jar, Cabosil™ TS-610 fumed silica was slurried in toluene until well dispersed, then a 10 % solution by weight of MAO in toluene was added. The mixture was stirred magnetically 15 minutes, then the MLC-5 or MLC-6 was added to the slurry, the mixture was stirred for 10 minutes, then the MLC-3 was added to the resulting slurry, and the mixture was stirred for 20 minutes. The mixture was spray-dried using a Buchi Mini Spray Dryer B-290 with the following parameters to yield the dried sample: Set Temperature: 140 °C, Outlet Temperature: 75 °C (min.), aspirator setting of 60 rotations per minute (rpm), and pump speed of 130 rpm. Table 1 contains the amounts of the metal-ligand complex, fumed silica, 10% MAO solution, and toluene used to make each of the spray-dried catalyst systems. Table 1: Quantities of MLC and reagents to make spray-dried supported catalyst systems SD-SCS-1 through -885976-WO-PCT / DOW 85976 WO

[0196] Supported catalyst samples SD-SCS-9 through -13 were made as follows. In a nitrogen-purged glove box, SD-SCS-2 was added into a 10 mL Parr Bomb, and then anhydrous deoxygenated toluene was added to create a slurry. Then, a hexanes solution of the unsupported metallocene MLC-7 (0.0005 M) was then added to that slurry and mixed to make the supported catalyst composition. After mixing for a certain amount of contact time (see Table 2), the supported catalyst samples, SD-SCS-9 through -13, were then used in polymerizations in a gas-phase reactor. The amounts of SD-SCS-2, toluene, MLC-7, and mixing time to make each supported catalyst composition are shown in Table 2. Table 2: Quantities of MLC and reagents to make supported catalyst systems SD-SCS-9 through -13

[0197] Gas-Phase Batch Reactor Test

[0198] The spray-dried catalysts and supported catalyst systems prepared above were used for ethylene / 1-hexene co-polymerizations conducted in the gas-phase in a 2-liter semi-batch stainless steel autoclave polymerization reactor equipped with a mechanical agitator.

[0199] For the experimental runs, the reactor was first dried, or “baked out,” for 1 hour by charging the reactor with 400 g of NaCl and heating at 105 °C under nitrogen for 60 minutes. After baking out the reactor, 5 g of spray-dried methyl aluminoxane (SDMAO) was introduced as a scavenger under nitrogen pressure. After adding SDMAO, the reactor was85976-WO-PCT / DOW 85976 WO sealed, and components were stirred. The reactor was then charged with hydrogen and 1- hexene pressurized with ethylene. Once the system reached a steady state, the spray-dried catalyst was charged into the reactor at 80 °C to start polymerization. The reactor was brought to the desired reaction temperature and maintained at this temperature, while keeping the ethylene, 1-hexene, and hydrogen feed ratios consistent throughout the 1 hour run. At the end of the run, the reactor was cooled down, vented, and opened. The resulting product mixture was washed with water and methanol, then dried. Polymerization activity or productivity (grams polymer / gram catalyst-hour) and polymerization efficiency (grams polymer / gram metal (Zr, Hf, or Ti)) was determined as the ratio of polymer produced, based on ethylene and hexene uptake / consumption, compared to the amount of catalyst added to the reactor.

[0200] The gas-phase batch reactor test was carrired out using each of comparative spray-dried catalyst samples SD-SCS-1 through -4, each of inventive spray-dried catalyst samples SD-SCS-5 through -8, and each of the inventive supported catalyst systems SD-SCS- 9 through -13. The performance of each of the supported and spray-dried catalyst systems was evaluated in terms of catalyst productivity, yield of washed polymer, polymer melt flow (I2, I21), melt flow ratio (MFR, I21 / I2), C6 uptake, weight average molecular weight (Mw), molecular weight of the highest peak or peak maxima (Mp), polydispersity index (PDI, Mw / Mn (wherein Mn is the number average molecular weight)), comonomer incorporation wt% (end group corrected), and melt temperature (Tm), the results of which are shown in Tables 3 and 4. Calculated amounts of deactivated phosphinimine catalyst are shown in Table 5. Table 3: Catalyst productivity, efficiency, and melt flow of polymers produced in gas-phase batch reactor85976-WO-PCT / DOW 85976 WO85976-WO-PCT / DOW 85976 WO*Batch reactor conditions: Temp. = X °C, C6 / C2 (molar ratio) = 0.0XX, H2 / C2 (molar ratio) = 0.00XX, C2PP = 220 psi, run time = 1 hr, catalyst injection temp. = 80 °C. NF = No Flow. N.D. = Not Determined.aRun time = 0.5 hr. Table 4: GPC, DSC & MWCDI data of polymers produced in gas-phase reactor85976-WO-PCT / DOW 85976 WO*Batch reactor conditions: Temp. = X °C, C6 / C2 (molar ratio) = 0.0XX, H2 / C2 (molar ratio) = 0.00XX, C2PP = 220 psi, run time = 1 hr, catalyst injection temp. = 80 °C. NF = No Flow. N.D. = Not Determined.aRun time = 0.5 hr.Table 5: Calculated PPM of Deactivated Phosphinimine85976-WO-PCT / DOW 85976 WO*Batch reactor conditions: Temp. = X °C, C6 / C2 (molar ratio) = 0.0XX, H2 / C2 (molar ratio) = 0.00XX, C2PP = 220 psi, run time = 1 hr, catalyst injection temp. = 80 °C. NF = No Flow. N.D. = Not Determined.aRun time = 0.5 hr.

[0201] Under industrially relevant high-, medium-, and low-density conditions, the productivities for inventive spray-dried dual catalyst systems SD-SCS-5 through -8 and supported catalyst systems SD-SCS-9 through -13 were consistently high, reaching as high as 49,500 gPE / gCat / hr. Each of the inventive spray-dried dual catalyst systems SD-SCS-5 through -7 employ a combination of MLC-3, a titanium catalyst possessing a combination of a pentafluorophenyl substituted cyclopentadiene and a tri-tert-butylphosphinimine, and MLC-5, a zirconium metallocene wherein one of the ligands contains a substituted indenyl. SD-SCS-8 employs a combination of MLC-3 and MLC-6, a hafnium metallocene wherein each cyclopentadienyl ligand is substituted with an alkyl group (n-propyl). SD-SCS-9 through -13 employs a combination of MLC-2, a titanium catalyst possessing a combination of a pentafluorophenyl substituted cyclopentadiene and a tri-tert-butylphosphinimine, and MLC-7, a Ge-bridged hafnium metallocene wherein each cyclopentadienyl ligand is85976-WO-PCT / DOW 85976 WO substituted with an alkyl group (n-propyl). The melt flow data and GPC data shows that under these commercially relevant process conditions, the inventive supported and spray-dried dual catalyst systems can produce ethylene / hexene copolymers with a range of weight average molecular weights (based on melt index measurements and GPC), in some instances, with fractional melt index (I2< 0.5 dg / min) capability, and in other cases with high Mw as indicated by the no flow measurements for the I2, and especially the I21, as well as by GPC data indicated in Table 4.

[0202] For SD-SCS-5 through -8, the broad melt flow ratios indicate the resins produced have a broad molecular weight distribution, which is either a broad unimodal or bimodal polymer as also observed by GPC. Also, as indicated by hexene consumed in the reactor compared to ethylene consumed (C6uptake, Table 3), GPC and DSC, these catalysts can produce ethylene / hexene copolymers with a range of densities (low to high, i.e., 0.910 g / cm3to 0.970 g / cm3) under prototypical gas-phase high-to-low density conditions. Also, the resins produced by each of the dual catalyst systems, SD-SCS-5 through -13 have an MWCDI > 0.0 indicating reverse short chain branching distribution or BOCD, with measured MWCDI as high as 6.5. Further, each of the dual catalyst systems SD-SDS-5 through -9 demonstrates the ability to produce ethylene copolymers having reverse short chain branching distribution in combination with broad Mz / Mw (e.g., Mz / Mw ≥ 3.0) and high productivity. The combination of high productivity and capability to produce ethylene copolymer with a range of M.I., or Mw, combined with broad MFR, broad Mz / Mw, and consistent reverse short chain branching distribution at high-to-low densities under prototypical gas-phase process conditions makes these catalysts important for a variety of multi-catalyst applications that produce ethylene copolymers with advantageous properties.

[0203] MEASUREMENT STANDARDS

[0204] Melt Index

[0205] Melt index (I2) was measured in accordance with ASTM 1238, condition B which is incorporated herein by reference in its entirety, 190 °C / 2.16 kg, and was reported in grams eluted per 10 minutes. High load melt flow index I21was measured in accordance with ASTM 1238, Condition B (190 °C / 21.6 kg), and was reported in grams eluted per 10 minutes.

[0206] Comonomer Consumption or Uptake85976-WO-PCT / DOW 85976 WO

[0207] 1-hexene consumption (%) was determined using the ratio of the amount of hexene consumed (grams) to amount of ethylene consumed (grams) in the gas-phase reactor over the course of the 1 hour experiment, and then multiplying that ratio by 100.

[0208] Melt Temperature

[0209] Melt temperature was determined via Differential Scanning Calorimetry according to ASTM D3418-08, which is incorporated herein by reference in its entirety. 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.

[0210] Mw, Mn, Mp, Mz, and Polydispersity Index (Mw / Mn) were determined by GPC. Mp is reported as the molecular weight of the peak maxima.

[0211] GPC measurements were performed as follows.

[0212] Compositional Conventional GPC

[0213] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5) and 4-capillary viscometer (DV) coupled to a Precision Detectors (Now Agilent Technologies) 2-angle laser light scattering (LS) detector Model 2040. For all absolute Light scattering measurements, the 15-degree angle is used for measurement. The autosampler oven compartment was set at 165 ºC and the column compartment and detectors were set at 155 ºC. The columns used were 4 TOSOH TSKgel GMHHR-H (30) HT 30-micron particle size, mixed pore size columns. The chromatographic solvent used was 1,2,4 trichlorobenzene and contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters and the flow rate was 1.0 milliliters / minute.

[0214] Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 g / mol and were arranged in 6 “cocktail” mixtures with at least a decade of separation between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. Individually prepared polystyrene standards of 10,000,000 and 15,000,000 g / mol, both from Agilent Technologies, were also prepared, at85976-WO-PCT / DOW 85976 WO 0.5 and 0.3 mg / mL respectively. The polystyrene standards were pre-dissolved at 80 ºC with gentle agitation for 30 minutes then cooled and the room temperature solution is transferred cooled into the autosampler dissolution oven at 160 ºC for 30 minutes. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).:(Equation 1)

[0215] where M is the molecular weight, A has a value of 0.4315 and B is equal to 1.0. A third order polynomial was used to fit the respective polyethylene-equivalent calibration points.

[0216] The total plate count of the GPC column set was performed with decane which was introduced into blank sample via a micropump controlled with the PolymerChar GPC-IR system. The plate count for the chromatographic system should be greater than 12,000 for the 4 TOSOH TSKgel GMHHR-H (30) HT 30-micron particle size, mixed pore size columns.

[0217] Samples were prepared in a semi-automatic manner with the PolymerChar “Instrument Control” Software, wherein the samples were weight-targeted at 1 mg / ml, and the solvent (contained 200ppm BHT) was added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples were dissolved for 3 hours at 165º Celsius under “low speed” shaking.

[0218] The calculations of Mn(GPC), Mw(GPC),and Mz(GPC)were based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 2-4, using PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve for the point (i) from Equation 1.85976-WO-PCT / DOW 85976 WO

[0219] In order to monitor the deviations over time, a flowrate marker (decane) was introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system. This flowrate marker (FM) was used to linearly correct the pump flowrate (Flowrate(nominal)) for each sample by RV alignment of the respective decane peak within the sample (RV(FM Sample)) to that of the decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the decane marker peak are then assumed to be related to a linear-shift in flowrate (Flowrate(effective)) for the entire run. After calibrating the system based on a flow marker peak, the effective flowrate (with respect to the narrow standards calibration) is calculated as Equation 5. Processing of the flow marker peak was done via the PolymerChar GPCOne™ Software. Acceptable flowrate correction is such that the effective flowrate should be within + / -0.5% of the nominal flowrate. Flowrate(effective)= Flowrate(nominal)* (RV(FM Calibrated) / RV(FM Sample)) (Equation 5)

[0220] Triple Detector GPC

[0221] For the determination of the viscometer and light scattering detector offsets from the IR5 detector, the Systematic Approach for the determination of multi-detector offsets is done in a manner consistent with that published by Balke, Mourey, et. al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)), optimizing triple detector log (MW and IV) results from a linear homopolymer polyethylene standard (3.5 > Mw / Mn > 2.2) with a molecular weight in the range of 115,000 to 125,000 g / mol to the narrow standard column calibration results from the narrow standards calibration curve using PolymerChar GPCOne™ Software.85976-WO-PCT / DOW 85976 WO

[0222] The absolute molecular weight data was obtained in a manner consistent with that published by Zimm (Zimm, B.H., J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)) using PolymerChar GPCOne™ software. The overall injected concentration, used in the determination of the molecular weight, was obtained from the mass detector area and the mass detector constant, derived from a suitable linear polyethylene homopolymer, or one of the polyethylene standards of known weight-average molecular weight. The calculated molecular weights (using GPCOne™) were obtained using a light scattering constant, derived from one or more of the polyethylene standards mentioned below, and a refractive index concentration coefficient, dn / dc, of -0.104. Generally, the mass detector response (IR5) and the light scattering constant (determined using GPCOne™) should be determined from a linear standard with a molecular weight in excess of about 50,000 g / mole. The viscometer calibration (determined using GPCOne™) can be accomplished using the methods described by the manufacturer, or, alternatively, by using the published values of suitable linear standards, such as Standard Reference Materials (SRM) 1475a (available from National Institute of Standards and Technology (NIST)). A viscometer constant (obtained using GPCOne™) is calculated which relates specific viscosity area (DV) and injected mass for the calibration standard to its intrinsic viscosity. The chromatographic concentrations are assumed low enough to eliminate addressing 2nd viral coefficient effects (concentration effects on molecular weight).

[0223] The absolute weight average molecular weight (MW(Abs)) is obtained (using GPCOne™) from the Area of the Light Scattering (LS) integrated chromatogram (factored by the light scattering constant) divided by the mass recovered from the mass constant and the mass detector (IR5) area. The molecular weight and intrinsic viscosity responses are linearly extrapolated at chromatographic ends where signal to noise becomes low (using GPCOne™). Other respective moments, Mn(Abs) and Mz(Abs) are be calculated according to Equations 6–8 as follows :85976-WO-PCT / DOW 85976 WO

[0224] The comonomer distribution in an poly(ethylene-co-1-alkene) copolymer can be characterized as either normal (also referred to as having a Zeigler-Natta distribution), reverse, or flat. Several reported methods are utilized to quantify a Broad Orthogonal Composition Distribution (BOCD). Herein, a simple line fit is utilized such that the normal or reverse nature of the comonomer distribution can be quantified by the molecular weight comonomer distribution index (MWCDI), which is the slope of the linear regression of the comonomer distribution taken from a compositional GPC measurement, wherein the x-axis is Log(MW) and the y-axis is weight percent of comonomer. Short chain branching (SCB) was excluded from the MWCDI calculation according to the formula 0.05 > (SCBF)*(MW detector response) wherein SCBF is the SCB frequency measured in SCB / 1000C. A reverse comonomer distribution is defined when the MWCDI > 0 and a normal comonomer distribution is defined when the MWCDI < 0. When the MWCDI = 0 the comonomer distribution is said to be flat. Additionally, the MWCDI quantifies the magnitude of the comonomer distribution. Comparing two polymers that have MWCDI > 0, the polymer with the greater MWCDI value is defined to have a greater, i.e., increased, BOCD; in other words, the polymer with the greater MWCDI value has a greater reverse comonomer distribution. Polymers with a relatively greater MWCDI, i.e., BOCD, can provide one or more improved physical and / or mechanical properties, such as melt strength, dart, and environmental stress crack resistance, when compared to polymers having a relatively lesser MWCDI.

[0225] The comonomer content (C6 wt%), e.g., 1-hexene, incorporated in the polymers was determined by rapid FT-IR spectroscopy on the dissolved polymer in a GPC measurement. Comonomer content was determined with respect to polymer molecular weight by use of an infrared detector (an IR5 detector) in a gel permeation chromatography measurement, as described in Analytical Chemistry 2014, 86(17), 8649-8656. “Toward Absolute Chemical85976-WO-PCT / DOW 85976 WO Composition Distribution Measurement of Polyolefins by High-Temperature Liquid Chromatography Hyphenated with Infrared Absorbance and Light Scattering Detectors” by Dean Lee, Colin Li Pi Shan, David M. Meunier, John W. Lyons, Rongjuan Cong, and A. Willem deGroot. Analytical Chemistry 201486 (17), 8649-8656.

[0226] It should be apparent to those skilled in the art that various modifications can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the specification cover modifications and variations of the described embodiments provided such modification and variations come within the scope of the appended claims and their equivalences.

[0227] Reference throughout this specification to “one embodiment,” “embodiments,” “certain embodiments,” “some embodiments,” “various embodiments,” “one or more embodiments,” or “an embodiment” means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure. Thus, the appearances of the phrases such as “in embodiments,” “in one or more embodiments,” “in certain embodiments,” “in various embodiments,” “in one embodiment,” “in some embodiments,” or “in an embodiment” in various places throughout this specification are not necessarily referring to the same embodiment. Furthermore, the particular features, structures, materials, or characteristics described in connection with one embodiment may be combined in any suitable manner in one or more other embodiments.

Claims

85976-WO-PCT / DOW 85976 WO CLAIMS1. A supported catalyst system comprising a support material, an activator, a phosphinimine procatalyst of formula (I), and a metallocene procatalyst of one of formulas (IIa)–(IIc):(I) (IIa) (IIb) (IIc) wherein: each M is independently titanium, zirconium, or hafnium; A is (C1–C20)heterohydrocarbylene, (C1–C20)hydrocarbylene, or a group comprising one or more heteroatoms independently selected from –Si(RC)2– and –Ge(RC)2–; each X is a monodentate ligand independently selected from (C1−C20)hydrocarbyl, (C1−C20)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, halogen, B(RY)4, Al(RY)4, Ga(RY)4, and –H, wherein: each RCis independently (C1−C20)hydrocarbyl, (C1−C20)heterohydrocarbyl, or –H; each Q is 0, 1, 2 or 3; each W is 0, 1, or 2; each RYis independently (C1−C20)hydrocarbyl, halogen, or –H; and optionally, in one or more of formulas (I) and (IIa)–(IIc), two X ligands are covalently connected to form a metallacycle ring;85976-WO-PCT / DOW 85976 WO R1–3are independently selected from (C1−C10)hydrocarbyl, (C1–C10)heterohydrocarbyl, and –H, with any two of R1–3optionally covalently connected to form a non-aromatic ring; and R4–33are independently selected from (C1-C10)hydrocarbyl, (C1–C10)heterohydrocarbyl, (C6–C20)aryl, (C3–C20)heteroaryl, and –H, wherein: any two of R4–8are optionally covalently connected to form a ring; any two of R9–13are optionally covalently connected to form a ring; any two of R14–18are optionally covalently connected to form a ring; any two of R19–25are optionally covalently connected to form a ring; any two of R26–29are optionally covalently connected to form a ring; and any two of R30–33are optionally covalently connected to form a ring.

2. The supported catalyst system of claim 1, wherein the support material comprises silica or fumed silica.

3. The supported catalyst system of claim 1 or 2, wherein the activator comprises methylalumoxane (MAO).

4. The supported catalyst system of any one of the preceding claims, wherein a molar ratio of metal in the activator to the combined metal in the phosphinimine procatalyst and the metallocene procatalyst is from 0.5:1 to 3,500:

1.

5. The supported catalyst system of any one of the preceding claims, wherein each X in one or more of formulas (I) and (IIa)–(IIc) is independently methyl or halogen.

6. The supported catalyst system of any one of the preceding claims, wherein at least one of R1, R2, and R3is (C1–C10)alkyl, or at least one of R1, R2, and R3is phenyl, or combinations thereof.

7. The supported catalyst system of any one of the preceding claims, wherein at least one of R4–8is an aryl or heteroaryl group.

8. The supported catalyst system of claim 7, wherein the at least one of R4–8is an aryl group that is substituted with one or more halogens.85976-WO-PCT / DOW 85976 WO 9. The supported catalyst system of any one of the preceding claims, wherein M in formula (I) is titanium and M in each of formulas (IIa)–(IIc) is zirconium or hafnium.

10. The supported catalyst system of any one of the preceding claims, wherein A is the group comprising one or more heteroatoms independently selected from –Si(RC)2– and –Ge(RC)2–.

11. The supported catalyst system of any one of the preceding claims, wherein R9–33are independently (C1−C8)alkyl or –H.

12. The supported catalyst system of any one of the preceding claims, wherein: one of R9–13is (C1–C8)alkyl and the remaining R9–13are –H; and one of R14–18is (C1–C8)alkyl and the remaining R14–18are –H.

13. The supported catalyst system of any one of claims 1–11, wherein: one of R9–13is (C1–C8)alkyl and the remaining R9–13are –H; and two of R19–25are independently (C1–C8)alkyl and the remaining R19–25are –H.

14. The supported catalyst system of any one of the preceding claims, wherein: one of R26–29is (C1–C8)alkyl and the remaining R26–29are –H; and one of R30–33is (C1–C8)alkyl and the remaining R30–33are –H.

15. A method of making the supported catalyst system of any one of the preceding claims, the method comprising spray-drying a mixture comprising an inert hydrocarbon liquid, the support material, the activator, the phosphinimine procatalyst, and the metallocene procatalyst to make the supported catalyst system.

16. A method making the supported catalyst system of any one of claims 1–14, the method comprising steps (a) and (b), or steps (c) and (d), or steps (e) and (f), or steps (g) and (h): (a) spray drying a mixture comprising an inert hydrocarbon liquid, the support material, the activator, and the phosphinimine procatalyst to make a spray-dried supported phosphinimine catalyst, and85976-WO-PCT / DOW 85976 WO (b) contacting the metallocene procatalyst with the spray-dried supported phosphinimine catalyst in an inert hydrocarbon liquid to make the supported catalyst system; or (c) spray drying a mixture comprising an inert hydrocarbon liquid, the support material, the activator, and the metallocene procatalyst to make a spray-dried supported metallocene catalyst, and (d) contacting the phosphinimine procatalyst with the spray-dried supported metallocene catalyst in an inert hydrocarbon liquid to make the supported catalyst system; or (e) spray drying a mixture comprising an inert hydrocarbon liquid, the support material, and the activator to make a spray-dried supported activator, and (f) contacting the phosphinimine procatalyst and the metallocene procatalyst with the spray-dried supported activator in an inert hydrocarbon liquid to make the supported catalyst system; or (g) spray drying a mixture comprising an inert hydrocarbon liquid, the support material, the activator, the phosphinimine procatalyst, and the metallocene procatalyst to make a spray-dried supported catalyst, and (h) contacting the spray-dried supported catalyst with additional phosphinimine procatalyst of formula (I) or additional metallocene procatalyst any one of formulas (IIa)–(IIc) to make the supported catalyst system.

17. A method of making a poly(ethylene-co-1-alkene) copolymer comprising polymerizing, via gas-phase polymerization, ethylene monomer, or a combination of ethylene monomer and at least one 1-alkene comonomer, in the presence of the supported catalyst system of any of claims 1-16.

18. The poly(ethylene-co-1-alkene) copolymer produced from the method of claim 17.

19. A poly(ethylene-co-1-alkene) copolymer comprising: from 50 to 99.9 wt% units derived from ethylene monomer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer; from 1 to 50 wt% units derived from at least one 1-alkene comonomer, based on the total weight of the poly(ethylene-co-1-alkene) copolymer;85976-WO-PCT / DOW 85976 WO from 0.0001 ppm to 10,000 ppm deactivated derivative of the phosphinimine procatalyst of any one of claims 1–14, based on the total weight of the poly(ethylene-co-1-alkene) copolymer; a weight average molecular weight from 30,000 to 400,000 g / mol; a melt temperature from 70 to 135 °C; a melt index (I2) from 0 to 400 dg / min; a high load melt flow index (I21) from 1 to 2,000 dg / min; a polydispersity index ≥ 3.0; a Mz / Mw ≥ 3.0; and a reverse short chain branching distribution or broad orthogonal composition distribution, as measured by an MWCDI > 0.0.

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