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

Abstract

Spray-dried 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 spray-dried catalyst system comprises a support material, an activator, and phosphinimine procatalyst of formula (I): (I) wherein: M is titanium, zirconium, or hafnium; each X is a monodentate ligand; and R1–8 are independently selected from (C1−C20)hydrocarbyl, (C1–C20)heterohydrocarbyl, and –H, provided that: at least one of R4–8 is an aryl group; or at least two of R4–8 are covalently connected to form a non-aromatic ring or multi-ring structure.

Description

86003-WO-PCT / DOW 86003 WO GROUPIV PHOSPHINIMINECYCLOPENTADIENYLSPRAY-DRIEDCATALYSTSYSTEMS FORMAKINGPOLY(ETHYLENE-CO-1-ALKENE)IN AGAS-PHASEPOLYMERIZATIONREACTORCROSS-REFERENCETORELATEDAPPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 652,885 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 spray-dried catalyst systems for olefin polymerization and, more particularly, to spray-dried 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 with86003-WO-PCT / DOW 86003 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. Also, supported catalyst systems that can produce polyethylene resins with fractional melt index (I2 ≤ 0.5 dg / min) at a range of density targets (i.e., under process amenable conditions for molecular catalysts in a gas-phase reactor, similar to prototypical conditions used for metallocenes, are of high interest for the gas-phase catalyst development.

[0006] It has now been discovered that spray-dried catalyst systems employing aryl-substituted cyclopentadienyl phosphinimine Group IV complexes have very high productivities and are capable of producing poly(ethylene-co-1-alkene) copolymers with a broad range of weight average molecular weights, including those with high molecular weights. These spray-dried catalysts exhibit high productivity and efficiency in gas-phase polymerization, 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). In addition, these catalysts are capable of producing polymers with a range of weight average molecular weights (Mw), including polymers with fractional melt indices (I2 ≤ 0.5 dg / min), as well as polymers with high comonomer86003-WO-PCT / DOW 86003 WO incorporation. Further, based on the observed hexene comonomer consumption, comonomer incorporation (wt% comonomer), and melt temperature of the polymer (Tm), these catalyst systems are able to produce resins with a range of densities.

[0007] Embodiments of this disclosure include spray-dried 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.

[0008] According to a first aspect of the present disclosure, a spray-dried catalyst system comprises a support material, an activator, and a phosphinimine procatalyst of formula (I):

[0009] In formula (I), M is titanium, zirconium, or hafnium; 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, two X ligands are covalently connected to form a metallacycle ring; and R1–8are independently selected from (C1−C20)hydrocarbyl, (C1–C20)heterohydrocarbyl, and –H, with any two of R1–3optionally covalently connected to form a non-aromatic ring, provided that:86003-WO-PCT / DOW 86003 WO at least one of R4–8is an aryl group, or at least two of R4–8are covalently connected to form a non-aromatic ring or multi-ring structure.

[0010] A second aspect includes the first aspect, wherein the support material comprises silica or fumed silica.

[0011] A third aspect includes any one of the first or second aspects, wherein activator comprises methylalumoxane (MAO).

[0012] A fourth aspect includes any one of the preceding aspects, wherein a molar ratio of metal in the activator to metal in the phosphinimine procatalyst is from 0.5:1 to 3,500:1.

[0013] A fifth aspect includes any one of the preceding aspects, wherein each X in one or more of formula (I) is independently methyl or halogen.

[0014] A sixth aspect includes any one of the preceding aspects, wherein at least one of R1, R2, and R3is (C1–C10)alkyl.

[0015] A seventh aspect includes the sixth aspect, wherein the at least one of R1, R2, and R3is tert-butyl.

[0016] An eighth aspect includes any one of the preceding aspects, wherein each of R1, R2, and R3is tert-butyl.

[0017] A ninth aspect includes the sixth aspect, wherein the at least one of R1, R2, and R3is a cycloalkyl group.

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

[0019] An eleventh aspect includes any one of the preceding aspects, wherein at least one of R4–8is (C6–C20)aryl, or at least two of R4–8are connected to form an unsaturated (C5–C20)cycloalkylene ring.

[0020] A twelfth aspect includes any one of the preceding aspects, wherein at least one of R4–8is pentafluorophenyl.

[0021] A thirteenth aspect includes any one of the preceding aspects, wherein M is titanium

[0022] According to a fourteenth aspect of the present disclosure, a method of making the spray-dried catalyst system of any one of the preceding aspects comprises: spray-drying a mixture comprising an inert hydrocarbon liquid, the support material, the activator, and the phosphinimine procatalyst; or spray-drying a mixture comprising an inert hydrocarbon liquid,86003-WO-PCT / DOW 86003 WO the support material, and the activator, thereby forming a spray-dried supported activator, and then contacting the phosphinimine procatalyst with the spray-dried supported activator in a second inert hydrocarbon liquid.

[0023] According to a fifteenth 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 spray-dried catalyst system of any one of the first through thirteenth aspects.

[0024] A sixteenth aspect of the present disclosure includes a poly(ethylene-co-1-alkene) copolymer produced from the method of the fifteenth aspect.

[0025] According to a seventeenth 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 a phosphinimine procatalyst of any one of the first through thirteenth aspects, based on the total weight of the poly(ethylene-co-1-alkene) copolymer.

[0026] 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. DETAILEDDESCRIPTION

[0027] 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.

[0028] Common abbreviations are listed below:

[0029] R, Z, M, X and n: as defined above; Me : methyl; Et : ethyl; Ph : phenyl; Ar : aryl; Bn: benzyl; 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 :86003-WO-PCT / DOW 86003 WO dichloromethane; CCl4 : carbon tetrachloride; EtOH : ethanol; CH3CN : acetonitrile; EtOAc : ethyl acetate; C6D6 : deuterated benzene or benzene-d6 : CDCl3 : deuterated chloroform; MeMgBr : methylmagnesium bromide; TiCl4 : titanium (IV) chloride N2 : nitrogen gas; PhMe: toluene; MAO : methylaluminoxane; MMAO : modified methylaluminoxane; PTFE : polytetrafluoroethylene; GC : gas chromatography; LC : liquid chromatography; NMR : nuclear magnetic resonance; HRMS: high resolution mass spectrometry; mmol : millimoles; mL : milliliters; M : molar; min: minutes; h : hours; d: days; equiv : equivalents.

[0030] 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.

[0031] 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.

[0032] 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.86003-WO-PCT / DOW 86003 WO

[0033] 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) 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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)).

[0038] 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,86003-WO-PCT / DOW 86003 WO 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. 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).

[0039] 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.

[0040] 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.

[0041] 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 adjacent86003-WO-PCT / DOW 86003 WO 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 include ethan-1,2-diyl (i.e. –CH2CH2–), propan-1,3-diyl (i.e. –CH2CH2CH2–), 2- methylpropan-1,3-diyl (i.e. –CH2CH(CH3)CH2–). Some examples of (C6–C50)arylene α,ω- diradicals include phenyl-1,4-diyl, napthalen-2,6-diyl, or napthalen-3,7-diyl.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] The term “heterohydrocarbon” refers to a molecule or molecular framework in which one or more carbon atoms are replaced with a heteroatom.

[0046] The term “(C1–C50)heterohydrocarbyl” means a heterohydrocarbon radical of from 1 to 50 carbon atoms, and the term “(C1–C50)heterohydrocarbylene” means a86003-WO-PCT / DOW 86003 WO heterohydrocarbon diradical of from 1 to 50 carbon atoms. The heterohydrocarbon of the (C1–C50)heterohydrocarbyl or the (C1–C50)heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl 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 two 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.

[0047] 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.

[0048] The term “heteroaromatic hydrocarbon” means an aromatic hydrocarbon molecule or molecular framework in which one to four carbon atoms are replaced with heteroatoms.

[0049] 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 4 to 12 carbon atoms) and being unsubstituted or substituted by one or more than one RS. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered 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. Examples86003-WO-PCT / DOW 86003 WO 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 system bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical can be a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6- ring system. An example of the fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1- yl. An example of the fused 5,6,6-ring system is 1H-benzo[f] indol-1-yl. An example of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of the fused 6,6,6-ring system is acrydin-9-yl.

[0050] 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.

[0051] 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.

[0052] 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−).

[0053] 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) one86003-WO-PCT / DOW 86003 WO 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.

[0054] 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).

[0055] Embodiments of the spray-dried catalyst systems described herein include a support material, an activator, and a phosphinimine procatalyst of formula (I):

[0056] In formula (I), M is titanium, zirconium, or hafnium; 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 RCis86003-WO-PCT / DOW 86003 WO independently (C1−C20)hydrocarbyl or (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, two X ligands are covalently connected to form a metallacycle ring; and R1–8are independently selected from (C1−C20)hydrocarbyl, (C1–C20)heterohydrocarbyl, and –H, with any two of R1–3optionally covalently connected to form a non-aromatic ring, provided that: at least one of R4–8is an aryl group; or at least two of R4–8are covalently connected to form a non-aromatic ring or multi-ring structure.

[0057] In embodiments, each X in formula (I) is independently methyl or halogen.

[0058] 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, each 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.

[0059] In embodiments, the at least one of R4–8in formula (I) that is an aryl group is substituted with one or more halogens. In embodiments, the at least one of R4–8in formula (I) is pentafluorophenyl.

[0060] In embodiments, M in formula (I) is titanium.

[0061] In specific embodiments of supported catalyst systems, the phosphinimine procatalyst according to formula (I) may be a metal-ligand complex having the structure of one of procatalysts MLC-1, MLC-2, or MLC-3:MLC-1 MLC-286003-WO-PCT / DOW 86003 WOMLC-3

[0062] Activator Component

[0063] In embodiments, the phosphinimine procatalyst of formula (I) may be rendered catalytically active by contacting it to, or combining it 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.

[0064] 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. In embodiments, the activator comprises methylalumoxane (MAO).86003-WO-PCT / DOW 86003 WO

[0065] 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.

[0066] A molar ratio of metal, e.g., aluminum, in the activator to Group IV metal in the phosphinimine may be 0.5:1 to 10,000:1, 0.5:1 to 7,000:1, 0.5:1 to 3,500:1, 0.5:1 to 1,500:1, 0.5:1 to 750:1, 0.5:1 to 300, 0.5:1 to 150:1, or 1:1 to 150:1. One or more embodiments provide that the molar ratio of metal in the activator to Group IV metal in the phosphinimine is at least 75:1. One or more embodiments provide that the molar ratio of metal in the activator to Group IV metal in the phosphinimine is at least 100:1. One or more embodiments provide that the molar ratio of metal in the activator to Group IV metal in the phosphinimine is at least 150:1. One or more embodiments provide that the molar ratio of metal in the activator to Group IV metal in the phosphinimine is at least 300:1. One or more embodiments provide that the molar ratio of metal in the activator to Group IV metal in the phosphinimine is at least 750:1. 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 independently may be a (C1–C8)alkyl, alternatively a (C1–C7)alkyl, alternatively a (C1–C6)alkyl, or alternatively a (C1–C4)alkyl.

[0067] Support Component

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

[0069] In embodiments, the procatalyst, the activator, or both, may be disposed on one or more support materials. For example, the procatalyst may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more support materials. The procatalyst, the activator, or both, may be combined with one or more support materials using one of the support methods well known in the art or as described below. As used in the present disclosure, the procatalyst, the activator, or both, may be in a86003-WO-PCT / DOW 86003 WO supported form, for example, when deposited on, contacted with, or incorporated within, adsorbed or absorbed in, or on, one or more support materials.

[0070] In 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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),86003-WO-PCT / DOW 86003 WO phyllosilicate, zeolites, talc, clays (e.g., as described in U.S. Patent No. 6,034,187), and mixtures of these. In other embodiments, combinations of these support materials may be used, such as, for example, silica-chromium, silica-alumina, silica-titania, and combinations of these. Additional support materials may also include those porous acrylic polymers described in European Patent No. 0 767 184. Other support materials may also include nanocomposites described in International Patent Application No. 1999 / 047598; aerogels described in International Patent Application No. 1999 / 048605; spherulites described in U.S. Patent No. 5,972,510; and polymeric beads described in International Patent Application No. 1999 / 050311. An example of a support material is fumed silica available under the trade name CABOSIL TS- 610, or other TS- or TG-series supports, available from Cabot Corporation. Fumed silica is typically a silica with particles 7 to 30 nanometers in size that have been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped.

[0075] 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.

[0076] 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.

[0077] 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 PQ86003-WO-PCT / DOW 86003 WO Corporation, e.g., ES70 product. The silica may be in the form of spherical particles, which may be obtained by a spray-drying process. Alternatively, MS3050 product is a silica from PQ Corporation that is not spray-dried. As procured, these silicas are not calcined (i.e., not dehydrated). Silica that is calcined prior to purchase may also be used as the support material.

[0078] 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.

[0079] 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.

[0080] Methods of Making Spray-Dried Catalysts Systems

[0081] As mentioned above, the phosphinimine procatalysts of formula (I) can be utilized to make spray-dried catalyst systems, i.e., spray-dried phosphinimine catalyst systems. As used herein, a “spray-dried” material refers to a material comprising components that have undergone a spray-drying process. Various spray-drying processes are known in the art and are suitable for forming the spray-dried catalyst systems disclosed herein.86003-WO-PCT / DOW 86003 WO

[0082] In one or more embodiments, the spray-drying process may comprise atomizing a composition including the phosphinimine procatalyst formula (I). 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.

[0083] The spray-dried catalyst systems disclosed herein may have the form of a free- flowing powder, for instance. After the spray-drying process, the spray-dried catalyst system and a number of known components may be utilized to form a slurry. The spray-dried catalyst system may be utilized with a diluent to form a slurry suitable for use in olefin polymerization, for example. In one or more embodiments, the slurry may be combined with one or more additional catalysts or other known components prior to delivery into a polymerization reactor.

[0084] 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 fumed silica (e.g. Cabosil) and methylaluminoxane (MAO), with a solution containing the phosphinimine procatalyst, sometimes called a trim solution. 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.

[0085] In some embodiments, methods for producing the spray-dried catalyst system include spray-drying a mixture comprising an inert hydrocarbon liquid, a support material, and an activator, thereby forming a spray-dried supported activator, and then contacting the phosphinimine procatalyst with the spray-dried supported activator in a second inert hydrocarbon liquid. Further embodiments include preparing a trim solution comprising the second inert hydrocarbon liquid and the phosphinimine procatalyst and then contacting the86003-WO-PCT / DOW 86003 WO trim solution with the spray-dried supported activator. In embodiments wherein a spray-dried supported activator is contacted with an inert hydrocarbon liquid and the phosphinimine procatalyst, 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.

[0086] 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.

[0087] Embodiments of the present disclosure also include methods of making spray-dried catalyst systems. In some embodiments, methods for making the spray-dried catalyst system include spray-drying a mixture comprising an inert hydrocarbon liquid, the support material, the activator, and the phosphinimine procatalyst. Spray-drying the mixture removes the inert hydrocarbon liquid to produce spray-dried particles, though spray-drying the mixture may not result in complete removal of liquids from the resulting catalyst system. That is, the spray-dried catalyst system may include residual amounts (i.e., from 1 wt% to 3 wt%) of the inert hydrocarbon liquid.

[0088] Polymerization Methods

[0089] As noted above, the spray-dried 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 spray-dried 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 at86003-WO-PCT / DOW 86003 WO least one 1-alkene comonomer in the presence of a spray-dried catalyst system described herein.

[0090] For example, in some embodiments, ethylene monomer and the at least one 1-alkene comonomer may be contacted with a spray-dried catalyst system of the present disclosure in a gas-phase polymerization reactor. The spray-dried catalyst system may be fed to the gas- phase polymerization reactor in neat form (i.e., as a dry solid) or as a slurry. For example, in some embodiments, spray-dried particles of the spray-dried catalyst system may be fed directly to the gas-phase polymerization reactor. In other embodiments, a slurry of the spray-dried catalyst system in an inert hydrocarbon liquid, such as an inert hydrocarbon or mineral oil, may be fed to the reactor.

[0091] 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.

[0092] 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-phase86003-WO-PCT / DOW 86003 WO 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 to 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.

[0093] 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).

[0094] 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 contemplated. 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 2,06886003-WO-PCT / DOW 86003 WO 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).

[0095] 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 the 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.

[0096] 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.

[0097] 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.

[0098] In one or more embodiments, the polymerization process produces greater than or equal to 2,500 grams of the polyethylene per grams of the spray-dried catalyst system per hour (gpoly / gcat·hour). In some embodiments, the process produces greater than or equal to86003-WO-PCT / DOW 86003 WO 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 35,000 gpoly / gcat·hour, or greater than or equal to 40,000 gpoly / gcat·hour.

[0099] Polyolefins

[0100] In embodiments, the spray-dried 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 spray-dried 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.

[0101] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a spray-dried catalyst system described herein has a weight average molecular weight of greater than or equal to 80,000 g / mol and less than or equal to 700,000 g / mol, greater than or equal to 100,000 g / mol and less than or equal to 700,000 g / mol, greater than or equal to 200,000 g / mol and less than or equal to 700,000 g / mol, greater than or equal to 300,000 g / mol and less than or equal to 700,000 g / mol, greater than or equal to 400,000 g / mol and less than or equal to 700,000 g / mol, greater than or equal to 500,000 g / mol and less than or equal to 700,000 g / mol, or greater than or equal to 600,000 g / mol and less than or equal to 700,000 g / mol.86003-WO-PCT / DOW 86003 WO

[0102] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a spray-dried 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 5 wt%, greater than or equal to 6 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%, greater than or equal to 12%, greater than or equal to 13%, greater than or equal to 14%, or greater than or equal to 15%.

[0103] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a spray-dried 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.

[0104] In embodiments, the poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a spray-dried 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%, or at least 15 wt% of the poly(ethylene-co-1-alkene) copolymer, based on a total weight of the poly(ethylene-co-1-alkene) copolymer. the86003-WO-PCT / DOW 86003 WO 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%, 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.

[0105] In embodiments, the poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a spray-dried 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.

[0106] The deactivated derivative of the phosphinimine procatalyst, as discussed herein, is made from a polymerization process, as discussed herein, which utilizes the spray-dried 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 spray-dried 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 spray-dried catalyst system.

[0107] In embodiments, the poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a spray-dried catalyst system described herein comprises deactivated derivative of the phosphinimine catalyst making up from 0.0001 ppm to 10,000 ppm, from 0.0001 ppm86003-WO-PCT / DOW 86003 WO 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.

[0108] 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 spray-dried catalyst system including a support material, an activator, a phosphinimine procatalyst of formula (I). In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a spray-dried catalyst system described herein has a density according to ASTM D792 (incorporated herein by reference in its entirety) from 0.870 g / cm3to 0.970 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.

[0109] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a spray-dried 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 or equal to 0.4 dg / min, less than or equal to 0.3 dg / min, or less than or equal to 0.25 dg / min.

[0110] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a spray-dried catalyst system described herein has a melt flow ratio (I21 / I2) of greater than or equal to 10, greater than or equal to 15, or greater than or equal to 18, 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).

[0111] In embodiments, a poly(ethylene-co-1-alkene) copolymer polymerized in the presence of a spray-dried catalyst system described herein has a melt index (I2) according of less than or equal to 0.5 dg / min and a catalyst productivity of greater than or equal to 10,000 gpoly / gcat·hour.

[0112] 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, primary86003-WO-PCT / DOW 86003 WO antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymers may contain any amounts of additives. The ethylene- based polymers may compromise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the ethylene-based polymers and the one or more additives. The ethylene-based polymers may further comprise fillers, which may include, but are not limited to, organic or inorganic fillers. The ethylene-based polymers may contain from about 0 to about 20 weight percent fillers such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the combined weight of the ethylene-based polymers and all additives or fillers. The ethylene-based polymers may further be blended with one or more polymers to form a blend.

[0113] 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.

[0114] Embodiments of the catalyst systems described in this disclosure yield unique polymer properties as a result of the high molecular weights of the polymers formed and the amount of the comonomers incorporated into the polymers.86003-WO-PCT / DOW 86003 WO

[0115] One or more features of the present disclosure are illustrated in view of the examples as follows: EXAMPLES

[0116] The structures of the metal-ligand complexes of inventive procatalysts MLC-1 to MLC-3 and comparative metal-ligand complexes CMLC-1 to CMLC-6 are shown below:

[0117] The synthesis procedures for inventive procatalysts MLC-1, MLC-2, and MLC-3 are provided below.86003-WO-PCT / DOW 86003 WO

[0118] 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%).

[0119] 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 2: Synthesis of MLC-286003-WO-PCT / DOW 86003 WO

[0120] 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 %).

[0121] 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 3: Synthesis of the trichloride intermediate to MLC-1 and -2

[0122] 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%).

[0123] 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),86003-WO-PCT / DOW 86003 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 4: Synthesis of the intermediate to MLC-1 and -2

[0124] 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%).

[0125] 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 5: Synthesis of the tri-tert-butylphosphinimine intermediate for MLC-1 and -2

[0126] 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%).

[0127] 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).86003-WO-PCT / DOW 86003 WO Example 6: Synthesis of an intermediate to MLC-3

[0128] In a N2-filled glovebox, a 20 mL vial was charged with the titanium precursor (246.4 mg, 0.66 mmol, 1 equivalents), 6 mL of toluene, and a stir bar. In a separate 20 mL vial, (2,8- dihydrodibenzo[e,h]azulen-2-yl)lithium1(157 mg, 0.66 mmol, 1 equiv.) was dissolved in 7 mL of toluene. The solution of the titanium precursor was added dropwise slowly to the lithium salt of the ligand at ambient temperature. The color of the reaction mixture changed from light yellow to dark brownish yellow upon addition of the titanium precursor. The reaction was stirred for 2 h at ambient temperature. The solvent was removed under vacuum. The solid yellow residue was washed with 1:1 hexanes:toluene (2 x15 mL). The yellow residue was filtered through a fritted funnel and dried under vacuum to afford a dark yellow powder (210 mg, 55%).

[0129] 1H NMR (500 MHz, C6D6) δ 7.63 (d, J = 6.7 Hz, 2H), 7.25 – 6.96 (m, 6H), 6.86 – 6.76 (m, 1H), 6.65 (d, J = 3.3 Hz, 2H), 4.80 (s, 1H), 3.74 (d, J = 14.0 Hz, 1H), 1.24 (d, J = 13.9 Hz, 4H), 1.14 (d, J = 13.7 Hz, 27H).13C NMR (126 MHz, C6D6) δ 139.86, 133.98, 132.50, 129.46, 129.19, 128.61, 128.35, 128.06, 127.97, 126.37, 111.67, 43.07, 42.20, 41.85, 39.27, 38.94, 29.51, 29.18.31P NMR (202 MHz, C6D6) δ 46.80. Example 7: Synthesis of MLC-3

[0130] In a N2-filled glovebox, a 20 mL vial was charged with the chloro complex (150 mg, 0.26 mmol, 1 equiv), 5 mL of toluene, and a stir bar. To the solution, MeMgBr in Et2O (0.21 mL of 3 M in Et2O, 0.62 mmol, 2.4 equiv) was added and the reaction mixture was stirred86003-WO-PCT / DOW 86003 WO for 30 mins at ambient temperature. The color of the reaction changes from yellow to dark brown upon addition of MeMgBr. The solution was filtered through a fritted funnel and a yellowish orange filtrate was obtained. The filtrate was evaporated under vacuum to obtain a light-yellow solid. To the light-yellow solid, 2 mL of toluene was added to dissolve the solid followed by addition of 1 mL of hexanes. The slurry was filtered through a fritted funnel to obtain a light-yellow filtrate, and concentrated to afford a light-yellow solid. The solid material was dissolved in 1 mL of toluene, and the liquid was then placed in glovebox freezer at -35°C for 3d. Faint yellow-colored crystal formation was observed after 3 days, and the mother liquor was removed from the vial. The crystals were washed with hexanes (2 x 3 mL), and dried under vacuum to afford the product as a faint yellow solid (61 mg, 45% yield).

[0131] 1H NMR (500 MHz, C6D6) δ 7.72 (d, J = 7.5 Hz, 2H), 7.22 (d, J = 7.4 Hz, 2H), 7.12 (q, J = 8.1, 7.4 Hz, 4H), 6.46 (d, J = 3.3 Hz, 2H), 6.07 (t, J = 3.6 Hz, 1H), 4.02 (d, J = 13.5 Hz, 1H), 3.81 (d, J = 13.6 Hz, 1H), 1.19 (d, J = 12.9 Hz, 28H), 0.57 (s, 6H).13C NMR (126 MHz, C6D6) δ 139.07, 129.02, 128.84, 128.35, 128.16, 127.96, 127.36, 126.76, 126.64, 108.77, 44.28, 43.02, 41.61, 41.25, 31.96, 29.19, 23.05, 14.33.31P NMR (202 MHz, C6D6) δ 33.07.

[0132] 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 internal86003-WO-PCT / DOW 86003 WO 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.

[0133] Procedure for Preparing Spray-Dried Catalyst Systems

[0134] Spray-dried catalyst samples SD-SCS-1 through -3 and SD-SCCS-1 through -6 were each prepared and sprayed in a nitrogen-purged glove box. In an oven-dried jar, hydrophobic fumed silica (Cabosil™ TS-610) was slurried in toluene until well dispersed, then a 10 % solution by weight of methylaluminoxane (MAO) in toluene was added. 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, fumed silica, 10% MAO solution, and toluene used to make each of the spray-dried catalysts. Table 1: Quantities of MLC and reagents to make the spray-dried supported catalyst systems

[0135] Gas-Phase Batch Reactor Test86003-WO-PCT / DOW 86003 WO

[0136] The spray-dried catalysts 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.

[0137] 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 supported methyl aluminoxane (SMAO) was introduced as a scavenger under nitrogen pressure. After adding SMAO, the reactor was 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 particle-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.

[0138] The gas-phase batch reactor test was carrired out using each of comparative spray- dried catalyst samples SD-SCCS-1 through -6 and each of inventive spray-dried catalyst samples SD-SCS-1 through -3. The performance of each of the spray-dried catalyst systems was evaluated in terms of catalyst productivity, catalyst efficiency, yield of washed polymer, and C6 uptake, the results of which are shown in Table 2. The performance of each of comparative spray-dried catalyst samples SD-SCCS-1 through -3 and -5, and each of inventive spray-dried catalyst samples SD-SCS-1 and -2, was further evaluated in terms of resulting polymer melt flow (I2, I21), melt flow ratio (MFR, I21 / I2), 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 Table 3. Calculated amounts of deactivated phosphinimine catalyst are shown in Table 4.86003-WO-PCT / DOW 86003 WO Table 2: Catalyst productivity, efficiency, and and hexene uptake in gas-phase batch reactor86003-WO-PCT / DOW 86003 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. Table 3: Melt flow, GPC, and DSC data of polymers produced in gas-phase batch reactor86003-WO-PCT / DOW 86003 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. Table 4: Calculated PPM of Deactivated Phosphinimine86003-WO-PCT / DOW 86003 WO

[0139] The productivities and efficiencies for inventive spray-dried catalysts SD-SCS-1 and -2, each of which is a titanium catalyst possessing a combination of a pentafluorophenyl-substituted cyclopentadiene and a tri-tert-butylphosphinimine, were consistently high under process relevant, industrially relevant high density and low-density conditions, with productivities reaching as high as 40,900 gPE / gCat / hr and efficiencies up to 17.1 MM gPE / gM. In contrast, comparative spray-dried catalysts SD-SCCS-1 through -6 were not able to consistently achieve high productivity, reaching only as high as 10,400 gPE / gCat / hr and efficiencies up to 4.3 MM gPE / gM (SD-SCCS-3), with some only achieving productivities between 50 and 250 gPE / gCat / hr (SD-SCCS-1 and -2). Inventive spray-dried catalyst SD-SCS-3, a titanium catalyst possessing a combination of a dihydrodibenzazulene and a tri-tert-butylphosphinimine, also demonstrated improved productivity and efficiency relative to comparative spray-dried catalysts SD-SCCS-1 through -6, achieving productivities as high as 16,200 gPE / gCat / hr and efficiencies up to 6.8 MM gPE / gM. The gas-phase polymerization results indicate that the presence of the aryl group on the cyclopentadiene of the phosphinimine procatalysts for SD-SCS-1 and -2), and the dihydrodibenzazulene group of the phosphinimine procatalyst for SD-SCS-3, are helpful for improving catalyst productivity and efficiency. Moreover, based on the melt flow data (I2, I21) and the GPC data, under these commercially relevant process conditions, these inventive spray-dried catalysts can produce ethylene / hexene copolymers with a range of weight average molecular weight (Mw), molecular weight distributions (Mw / Mn, PDI) in some instances, with fractional melt index (M.I.) capability, and in other cases with high Mw combined with higher comonomer incorporation than the comparative spray-dried examples.86003-WO-PCT / DOW 86003 WO

[0140] Also, as indicated by hexene consumed in the reactor compared to ethylene consumed (C6 uptake, Table 2) as well as the GPC and DSC data (Table 3), these catalysts also can produce ethylene / hexene copolymers with a range of incorporation and densities (low to high, i.e., 0.910 g / cm3– 0.960 g / cm3) under prototypical gas-phase high-to-low density conditions.

[0141] The combination of significantly higher productivity, efficiency, and capability to produce ethylene copolymers with fractional melt index at a range of Mw and comonomer incorporation, including high Mw and higher comomer incorporation than comparative examples, at high-to-low densities under prototypical gas-phase process conditions, makes these spray-dried catalysts important for a variety of both single and multi-catalyst applications that produce ethylene copolymers with advantageous properties.

[0142] MEASUREMENT STANDARDS

[0143] Melt Index

[0144] 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 I21 was measured in accordance with ASTM 1238, Condition B (190 °C / 21.6 kg), and was reported in grams eluted per 10 minutes.

[0145] Melt Temperature

[0146] 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.

[0147] Comonomer Consumption or Uptake

[0148] 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.

[0149] Mw, Mn, Mp, and Polydispersity Index (Mw / Mn) were determined by GPC. Mp is reported as the molecular weight of the peak maxima.

[0150] GPC measurements were performed as follows.

[0151] Compositional Conventional GPC86003-WO-PCT / DOW 86003 WO

[0152] 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.

[0153] 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, at 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)

[0154] 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.

[0155] 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-IR86003-WO-PCT / DOW 86003 WO 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.

[0156] 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.

[0157] 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.

[0158] 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 standards86003-WO-PCT / DOW 86003 WO 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)) (Equation5)

[0159] Triple Detector GPC

[0160] 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.

[0161] 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 linear86003-WO-PCT / DOW 86003 WO 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).

[0162] 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 :

[0163] 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.

[0164] Reference throughout this specification to “one embodiment,” “embodiments,” “certain embodiments,” “some embodiments,” “various embodiments,” “one or more86003-WO-PCT / DOW 86003 WO 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

86003-WO-PCT / DOW 86003 WO CLAIMS1. A spray-dried catalyst system comprising a support material, an activator, and a phosphinimine procatalyst of formula (I):wherein: M is titanium, zirconium, or hafnium; 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, two X ligands are covalently connected to form a metallacycle ring; and R1–8are independently selected from (C1−C20)hydrocarbyl, (C1–C20)heterohydrocarbyl, and –H, with any two of R1–3optionally covalently connected to form a non-aromatic ring, provided that: at least one of R4–8is an aryl group; or86003-WO-PCT / DOW 86003 WO at least two of R4–8are covalently connected to form a non-aromatic ring or multi-ring structure.

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

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

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

1.

5. The spray-dried catalyst system of any one of the preceding claims, wherein each X in one or more of formula (I) is independently methyl or halogen.

6. The spray-dried catalyst system of any one of the preceding claims, wherein at least one of R1, R2, and R3is (C1–C10)alkyl.

7. The spray-dried catalyst system of claim 6, wherein the at least one of R1, R2, and R3is tert-butyl.

8. The spray-dried catalyst system of claim 6, wherein the at least one of R1, R2, and R3is a cycloalkyl group.

9. The supported catalyst system of any one of claims 1–5, wherein at least one of R1, R2, and R3is phenyl.

10. The spray-dried catalyst system of any one of the preceding claims, wherein at least one of R4–8is (C6–C20)aryl, or at least two of R4–8are connected to form an unsaturated (C5–C20)cycloalkylene ring.86003-WO-PCT / DOW 86003 WO 11. The spray-dried catalyst system of any one of the preceding claims, wherein at least one of R4–8is pentafluorophenyl.

12. The spray-dried catalyst system of any one of the preceding claims, wherein M is titanium.

13. A method of making the spray-dried 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, and the phosphinimine procatalyst; or spray-drying a mixture comprising an inert hydrocarbon liquid, the support material, and the activator, thereby forming a spray-dried supported activator, and then contacting the phosphinimine procatalyst with the spray-dried supported activator in a second inert hydrocarbon liquid.

14. A method of making a poly(ethylene-co-1-alkene) copolymer comprising polymerizing, via gas-phase polymerization, ethylene monomer and at least one 1-alkene comonomer in the presence of the spray-dried catalyst system of any one of claims 1–13.

15. The poly(ethylene-co-1-alkene) copolymer produced from the method of claim 14.

16. 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; from 0.0001 ppm to 10,000 ppm deactivated derivative of a phosphinimine procatalyst of any one of claims 1–12, based on the total weight of the poly(ethylene-co-1-alkene) copolymer.

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